CMA
FLUOROCARBON RESEARCH PROGRAM
Effect of Chlorofluorocarbons on the Atmosphere
Revision
No. 21
The Fluorocarbon Research Program, sponsored and funded by the industry, is summarized in Revision 21, June 1, 1985. Underscoring indicates developments since Revision No. 20.
For additional information, please contact the investigator or CMA.
Sincerely,
Elizabeth Festa Gormley
Program Manager
Fluorocarbon Program
Telephone: 202/887-1194
Attachment: Revision
No.
21
June 13, 1985
CODE: 36-B
For Distribution by CMA
SPECIAL PROGRAMA DIVISION
From E. Testa Gormley
RA No. EPP 106-AQ
Date- 6/4/85
L
Formerly Mnufacturing Chemists Association-serving Chemical Industry Since 1872.
2501 M Street, NW * Washington, DC 20037 * Telephone 202/887.1 too * Telex 89617 (CMA WSH)

SUMMARY
Research Program on
EFFECT OF CHLOROFLUOROCARBONS ON THE ATMOSPHERE
Sponsored by the Chlrofluorocarbon Industry
Prepared by: B. Peter Block
Hillel Magid
Distributed by:
Richard B. Ward
Chemical Manufacturers Association
2501 M Street, N.W.
Washington, D. C. 20037
(Originally Issued: September 26, 1975)
Revision No. 21: June 1, 1985

TABLE OF CONTENTS
Page
Summary and Recommendations
The Industry-Sponsored Program
Assessments of the Science
Efforts to Resolve Current Uncertainties
Tables:
1 Chlorofluorocarbon Manufacturers Represented on the CMA Technical Panel on Chlorofluorocarbon
Research
2 Chlorofluorocarbon Research Program - Financial
Summary
3 Chlorofluorocarbon Research Program - Types of
Research Activities, Summaries
A. investigation of Reaction Rates,
Products, and Mechanisms
B.
Source and Sink Studies
C. Laboratory Studies Related to Potential
Atmospheric Measurements
D.
Tropospheric and Stratospheric Measurements
E. Modeling
F. Other
G. Consultants
4A CMA FPP Projects - Work Completed 77
4B CLMA FPP Projects - Work in Progress 92
5 Publications from Work Supported by Chlorofluoro carbon Manufacturers 98 to Table 3 by Investigator and Project Number 125 ii
12
26
35
47
64
70
75
10
11
12
1
2
4
5

SUMMARY
Research Program on
EFFECT OF CHLOROFLUOROCARBONS ON THE ATMOSPHERE
Sponsored by the Chlorofluorocarbon Industry
Administered by the Chemical Manufacturers Association
(originally Issued: September 26, 1975)
Revision No. 21: June 1, 1985
This summary describes work supported by the manufacturers of chlorofluorocarbons (CFCs, sometimes called fluorocarbons) in an attempt to assess the possible impact of these chemicals on the environment and, in particular, on the stratospheric ozone layer.
Summary and Recommendations
In 1972 the CFC manufacturers began supporting a program to investigate the effects of CFCs on the environment. This program has been expanded greatly to help determine the extent, if any, to which these compounds may affect the stratospheric ozone layer. Industry- and government-sponsored scientists working on the halogen-ozone problem have cooperated effectively. Continuation of this cooperation is essential, with special attention to providing periodically updated summaries of research priorities, programs, and results, together with critical analyses of the reliability and significance of the data.
The programs now under way to develop methods for determining the ozone changes that are actually occurring (as opposed to hypothetical or calculated ozone changes) and to resolve important

questions about key stratospheric species 0
3
, C10, total chlorine will lead to a progressively better understanding of the effect of the CFCs on stratospheric ozone.
The industry position continues to be:
• The ozone depletion theory warrants serious concern and continuing investigation.-
• The international scientific consensus necessary to resolve this issue must be based on convincing measurements and 'evaluations, not theory alone.
• Convincing experimental evidence can be obtained to verify or disprove the theory quantitatively.
• There is time to perform these necessary experiments without significant risk to the health and welfare of the population-
The Industry-Sponsored Program
In July of 1972, E. I. du Pont de Nemours & Company issued to CFC manufacturers worldwide an invitation to a "Seminar on the Ecology of
Fluorocarbons." Its purpose was to establish a technical program because, as stated in the invitation,
"Fluorocarbons are intentionally or accidentally vented to the atmosphere worldwide at a rate approaching one billion pounds per year. These compounds may be either accumulating in the atmosphere or returning to the surface, land or sea, in the pure form or as decomposition products. Under any of these alternatives, it is prudent that we investigate any effects which the compounds may produce on plants or animals now or in the future."
_ 2-

Representatives of 15 companies attended the meeting, agreed that such a program was important, and established and funded a CFC research program under the administration of the Chemical Manufacturers Association (CMA). Thus, in
1972, with no evidence that CFCs could harm the environment the producers of these chemicals agreed that there was a need for more information and proceeded to act.
The CFC producers supporting this program represent almost the total production of CFC& in the Americas, Western Europe, Japan, and Australia. The research is directed by the CMA Fluorocarbon Program Panel (FPP) with one voting member from each supporting company. This Panel meets regularly to review progress on current-research, evaluate new proposals, and exchange data with contractors, with government agencies, and with other scientists.
Publication of the Rowland-Molina hypothesis in 1974 identified a potentially serious problem, so the CMA FPP research program was expanded considerably. The CFC-ozone relationship attracted the attention of many scientists in academic and government laboratories, legislative and regulatory bodies, and the press. The CMA FPP program is concentrating on research most likely to answer the critical question: to what extent will human activities affect the stratospheric ozone layer, and, if they are a factor, to what extent are CFCs involved?
To strengthen the overall effort to find the answer, CMA FPP has coordinated its efforts with others working on the possible effects of emission of CFCs and other trace gases. These problems concern the federal government, and interactions with a number of agencies have been especially helpful in:
1. Taking advantage of the knowledge and experience gained in the Climatic
Impact Assessment Program;
2. Coordinating funding of programs addressing the environmental effects of trace gases;
-3-

3. Planning joint experiments with government research groups; and
4. Helping to set priorities-for industry-Sponsored research.
About 580 research proposals have been reviewed to date, and-projects totaling about $16.9 million-have been funded (see Table 2). Calendar 1995 commitments are expected to total almost $1.8 million and total expenditures through 1985 will be approximately $18.9 million.
Assessments of the Science
The Clean Air Act Amendments of 1977 (U. S. Public Law 9595) established the U. S. Environmental Protection Agency (EPA) as the agency responsible for assessing the probable effect of CFCs on the ozone layer. Other U. S. agencies are given various responsibilities in the-scientific effort required to support any decisions, and the EPA is required to rely on the National Academy of
Sciences (NAS) for advice on the status of the science. The NAS has issued several reports. The latest, by its Committee on Causes and Effects of Changes in Stratospheric Ozone: Update 1983, was released in February, 1984.* The present state of knowledge has also been assessed by the National Aeronautics and Space Administration (NASA)+ and the United Nations Environment
_______________________________
*Committee on Causes and Effects of Changes in Stratospheric Ozone: Update
1983, National Research Council, "Causes and Effects of Changes in
Stratospheric Ozone: Update 1983," National Academy of Sciences, Washington,
D.C., 1984. The pages in the reference where the research recommendations appear are identified by square brackets [ ].
+Present State of Knowledge of the Upper Atmosphere An Assessment Report,
National Aeronautics and Space Administration, January, 1984.
-4-

Programme Coordinating Committee on the Ozone Layer (,CCOL),++ the EPA has reported to Congress on the status of regulations in the United States to protect stratospheric ozone, X and the United Kingdom Royal Commission on
Environmental Pollution has commented on the current status of the
CFC-stratospheric ozone issue.
xx
Efforts to Resolve Current Uncertainties
The emphasis of the CMA-administered industry program has been overwhelmingly in the major areas recommended for further study by the different groups assessing the issue. The industry sponsored program, therefore, aims to fill in the most important gaps in existing scientific-knowledge. The following research recommendations identified by NAS* are, in whole or in part, the subject- of projects funded and cofunded by FPP and member companies. o More rate and photochemical parameters must be measured with high accuracy and with careful attention to the identification of product channels. o The rapid progress in experimental techniques must be maintained, new methods for the detection of reactive species developed, and larger ranges of temperature and pressure variation investigated. [Page 30]
_______________________________
++Environmental Assessment of Ozone Layer Depletion and its Impact as of
November, 1981, Bulletin No. 7, United Nations Environment Programme,
January-, 1982. The recommendations for future work were revised all meetings of CCOL April 5-8, 1983, and October 15-18, 1984. x Report to Congress on the Progress of Regulation to Protect Stratospheric
Ozone, U.S. Environmental Protection Agency, April, 1983. xx Tackling Pollution - Experience and Prospects, Royal Commission on
Environmental Pollution, Tenth Report, February, 1984.
*See p. 4 for footnote*.
-5-

o The long-term monitoring of the atmospheric concentrations of the source gases must be supported, because the worth of such data depends strongly an the continuity of the record. Particular emphasis should be placed on the integrity of standards, international intercomparison, and publication of the data, accompanied by documentation of the methodology. [Pages 48-91 o Instrumentation should be developed to measure ozone concentrations at 40 km with accuracy of a few percent so that there can-be early detection of trends at the altitude where the percentage ozone changes due to anthropogenic perturbations are calculated to be the largest relatively. A monitoring program should then be instituted. The thrust should be toward a combination of balloon and satellite sensors. o The development and field testing of instrumentation to measure a variety of stratospheric trace species should be supported strongly since many of the important species remain unmeasured or poorly measured. The primary goals should be the radical and reservoir species. o The discrepancies between C10 measurements taken with different techniques should be resolved as soon as possible. o Rigorous, double-blind intercomparisons of instruments in the field should be continued to assess the reliabilities of current technology, since this is the best way to assess accuracy. Support is critical during the difficult phase of this endeavor, namely, after differences have been demonstrated and rationalizations are then sought. o Intensive measurement campaigns should be mounted to deploy a group of multiple-species instruments that can determine the full data set required to test a proposed
-6-

hypothesis. The campaigns should include ground-based, balloon, aircraft, and satellite configurations. [Page 491 o The lower stratosphere. Efforts to evaluate the effects of transport and variability on the ozone budget of the lower stratosphere must be increased.
In light of the importance-of this-region in compensating for calculated ozone decreases in the photochemically controlled upper stratosphere, a quantitative understanding of the interaction of transport and chemistry in the lower stratosphere should be given very high priority . [Page 641 o It is important to validate and calibrate more accurately the existing 2-D models, since they should be able to simulate the seasonal and latitudinal behavior of ozone and other trace species in the current atmosphere. [Page 931 o The detection and prediction of trends in ozone are a focus of this report. It is now clear that efforts at verifying perturbations to the atmosphere should be directed toward the detection of changes in ozone in the upper stratosphere.-..The importance of tropospheric ozone, however, should not be ignored; we must also continue to model and observe significant changes in the lower atmosphere [Pages.93-41 o The overall effort at comparison of theory with observation must continue.
Especially promising are those studies that attempt to remove the noise in observational data that is associated with spatial variations. A more accurate calibration of local ozone concentrations of models with observations is important, especially as an aid to understanding the chemistry and dynamics of the lower stratosphere, an area of great uncertainty in the current models.
-7-

o A prime focus of the validation of photochemical models must continue to be the systematic collection of observa tional data that can define,-the local chemical systems as essential the simultaneous observation of several long short-lived species, for example, 0
HN0
3
, NO, N0
2 within the stratosphere. In this framework we regard and,
3
, 0, OH, H
2
0,
, Cl, and ClO. [Page - 94 - I o Emissions, inventories, and lifetimes should be defined for the key species that affect ozone, directly or indirectly, such as halocarbons, N
2
0, NO x
, CH
4
, and C0
2
. o Models that couple radiation, dynamics, and photochemistry in comparable detail should continue to be developed. Both the dynamical and the chemical mechanisms that couple the trace gases of the stratosphere and troposphere need to be examined. o The observational evidence for changes in stratospheric ozone over the past decade need to be evaluated and attempts to define similar trends in important background gases, such as N
2
0,NO x
,CH
4
, and other hydrocarbons, CO, and stratospheric H
2
0 should be continued. o Techniques need to be developed for the quantitative analysis of uncertainties in theoretical models particularly their sensitivity with regard to the chemical kinetic scheme and the parameterization of dynamical transport. [Page 1121 o Predictions of basal cell carcinomma and squamous cell carcinoma incidence based on epidemiological data must take into account social and demographic factors as well as changes in UV-B insolation. [Page
1671
The FPP-Also supports many of the areas of research included in the CCOL recommendations for future work,++ which overlap the
_____________________________________
++ See p. 5 for footnote ++ .

NAS recommendations to a considerable extent, as well as areas of research not-identified in either the NAS or CCOL recommendations (see Table 3).
Details on the CMA FPP program are given in Tables 3, 4A, and 4B. Table 3 lists summaries of the projects by type of research activity. -Table 4A.lists completed projects, and Table 4B lists active projects in chronological order of funding. Table 5 lists refereed publications resulting from industrysponsored work, plus selected reports issued by CMA. Additional written information is, in some cases, available from the individual investigators.
In addition to the work supported by the CFC industry at universities and other laboratories, there are studies underway in the laboratories of individual member companies who have scientists able to make significant contributions to the resolution of the problem. Problems receiving particular attention by industry scientists include: the application of statistical methods to detect abnormal trends in stratospheric ozone concentrations, the evaluation and development of modeling techniques, and the study of the sensitivity of models to various input parameters.
-9-

Table 1
CHLOROFLUOROCARBON MANUFACTURERS
Represented on the
CMA FLUOROCARBON PROGRAM PANEL
Akzo Chemie bv (Holland)
Allied Corporation (U.S.)
Asahi Glass Co., Ltd. (Japan)
ATOCHEM (France)*
Australian Fluorine Chemicals Pty. Ltd. (Australia)
Daikin Kogyo Co., Ltd. (Japan)
Du Pont Canada Inc. (Canada)
E. I.-du Pont de Nemours & Company, Inc. (U.S.)
Essex Chemical Corporation (Racon), (U.S.)
Hoechst AG (West Germany)
Imperial Chemical Industries PLC (England)
I.S.C. Chemicals Ltd. (England)
Kaiser Aluminum & Chemical Corporation (U.S.)
Kali-Chemie Aktiengesellschaft (West Germany)
Mitsui Fluorochemicals Co. Ltd. (Japan)
Montefluos - Gruppo Montedison (Italy)
Pennwalt Corporation (U.S.)
Showa Denko K. K. (Japan)
Societe des Industries Chimiques du Nord de la Grece,
S.A. (Greece)
Union Carbide Corporation (U.S.)**
June 1, 1985
__________________________________
*Has taken over chlorofluorocarbon activities of CHLOE Chemie and Ugine
Kuhlmann.
**Does not currently manuf acture chlorofluorocarbons. Supported the CMA program through June, 1977.
_10-
Table 2
CHLOROFLUOROCARBON RESEARCH PROGRAM

Administered by
Chemical Manufacturers Association
Financial Summary
Type of Activity a
Products, and Mechanisms
Completed
Projects Total
A. Investigation of Reaction Rates, $ 1,354,665 $915,782 $2,270,447
Active
Projects
B. Source and Sink Studies
C. Laboratory Studies Related to
Potential Atmospheric
Measurements
2,361,245
1,483,500
422,971 2,784,216
507,090 1,990,590
D. Tropospheric and Stratospheric
Measurements 2,893,936 2,491,451 5,385,387
E and F Modeling and Other Projects 3,229,285 822,693 4,051,978
G. Consulting 306,208 148,189 454,397
SUBTOTAL
Administrative Expenses
$11,628,839 $5,308,176 $16,937,015
1,381,693
TOTAL $18,318,708 a individual projects are summarized in Table 3.
June 1, 1985

Table 3*
Chlorofluorocarbon Research Program
Types of Research Activities, Summaries
A. Investigation of Reaction Rates, Products, and Mechanisms
Dr. R. ATKINSON -- University of California at Riverside -- 84-531.
Reactions of Gas-Phase Chlorine Nitrate with Water Vapor and Hydrogen
Chloride.
Atmospheric modeling calculations show that the title reactions could be important in E-h-e stratosphere even if they proceed at a relatively slow rate. Available gas-phase reaction rate data are limited and subject to uncertainties because both reactions appear to be strongly catalyzed by solid surfaces. In this study interference by such wall reactions will be minimized by the use of large reaction chambers with a low surface-to-volume ratio.
Dr. K. H. BECKER -- University of Wuppertal, F.R.G.--83-455. Pressure and Temperature Dependence of the Reaction of OH with H02NO2
(completed).
The reaction of OH with H0
2
NO
2
was studied at temperatures from 256 to 295
K at total pressures of N
2
or air ranging from 1 to 300 torr. Over the range of conditions investigated and within experimental error the reaction was found to be temperature and pressure independent. A value of (5.5 ±
0-5) x 10 -12cm3 /s was obtained for the rate constant for the reaction.
Product studies using wet chemical and photolytical methods for producing
H0
2
NO
2
suggest that its reaction with OH radicals leads to formation of H
2
0,
0
2
, and N0
2 with greater than 90% yield.
N0
2
+ 0
2
was studied
______________________________
*Significant changes since the last revision are underscored.
Reaction rate constants were measured using the discharge flow technique in combination with mass spectrometry for detection. The reaction NO + 0
3
-12-
Dr. J. W. BIRKS -- University of Illinois -- 75-1, 76-117A, 76-117B.
Measurement of Reaction Rates Relevant to the Fluorocarbon-Ozone
Problem; Studies of Heterogeneous Reactions (completed).

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms over the temperature range 203-361 K. The resulting Arrhenius expression is k = (2.34 ± 0.23) x 10 -12 exp(-1450+50/T) cm 3 molec -I s -1 and predicts k = 1.80 x
10 -14 at 298 K in excellent agreement with previous determinations. The activation energy, however, is 12%-higher than the previously accepted value. A slight curvature in the Arrhenius plot was observed, the activation energy increasing with increasing temperature.
The rate constant for the reaction C10 + N0
2
+ M -> ClN0
3
+ M was measured over the temperature range 250-356 K and the pressure range 1-5 torr by detecting the loss of C10 in a large excess of N0
2
The reaction was found to be third order with N
2
being twice as effective a third body as He. The low-pressure, third-order rate constant in N
2
is given by expression k = (4.40 ± 0.66) x
10 -33 exp(1087 70/T) cm 6 mole, S -1 .
No reaction Of ClON0
2
with NO NO
2
, 0
3
, or HC1 could be observed. Upper limits of
4 x 10 -17 , 2 x 10 -17 , 7 x 10 -17 and 1.2 x 10 -15 cm 3 molec -l s -1 for the respective bimolecular reaction rate constants rule out these reactions as significant sinks for ClON0
2
in the stratosphere.
The possibility of successive oxidation of C10 to perchloric acid was investigated. The reaction of CIO with 0
3
was too slow to measure. An upper limit of 1 x 10 -16 cm 3 molec -l s -l was established for the reaction C10 + 0
3
-->
OC10 + 0
2
, and an upper limit for the reaction C10 + 0
3
, C100 + 0
2
was found to be 5 x 10 -14 . Not only is OC10 formed slowly; the absorption spectrum was obtained, and the photolysis constant calculated to be 7.6 x 10 -2 s -1 , corresponding to a photolytic lifetime of 13 s. Furthermore, the reaction OC10
+ 0
3
-> C10
3
+ 0
2
is extremely slow, k << 1 x 10 -18 cm 3 molec -l s -1 at 298 K. These results rule out the importance of successive oxidation of chlorine to higher oxides as a path to the photochemically stable species, perchloric acid.
Exploratory studies of the heterogeneous reactions ClON0 and ClON0
2
+ H
2
+ HC1 w- C1
2
+ HON0
2
0 w HOC1 + HON0
2 on sulfuric acid coated walls resulted in
2 heterogeneous rate constants that are too small to be of significance in the stratosphere.
Dr. J. W. BIRKS -- University of Colorado -- 77-192, 78-244, 79-276,
80-321, 80-329, 82-425, 83-490; Drs. J. W. BIRKS and R. E. SIEVERS --
University of Colorado -81-358. ttudies of Reactions of Importance in the
Stratosphere.
-13-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
The rate constant for the reaction CIO + H0
2
-> HOC1 + 0
2
was measured by following the appearance of the HOC1 product. The rate constant is independent of pressure over the range 2-6 torr, the result being k = (4.5 ± 0.9) x 10 -12 cm 3 molec -l s -1 at 298 K. An upper limit of 2% for the branching ratio to the alternative products, HC1 + 0
3
, was established by attempting to detect ozone as a reaction product. The measured rate constants for this reaction at the elevated temperatures of 318 K 338 K, and 358 K are 3.8 x 10 -12 , 4.0 x 10 -12, and
3.8 x 10 -12 , respectively.
The reaction C1 + HOCI -> Products was studied over the temperature range
243-365 K by detecting the loss of HOC1 in a large excess of C1 atoms. The temperature-dependent rate constant is yiven by k = (3.0 ± 0.5) x 10 -12 exp[-(130 ± 60)/T] cm 3 molec -l s -1 . Both sets of products, HC1 + C10 and C1
2
+ OH, are possible. The products C1
2
+ OH are favored by consideration of the equilibrium constant for the reaction forming these products and the measured rate constant for the reverse reaction. Even if the reaction branches totally to HC1 + CIO, however, this reaction becomes important in the stratosphere only when the total Cl x
exceeds 10 ppbv.
Upper limits for the reactions HOC1 + NO - Products and HOC1 + 0
3
-> Products at 300 K were established to be 1 x 10 -17 and 4 x 10 -16 cm 3 molec -l s -1 ,espectively.
A new method for determining activation energies over temperature intervals as small as 10 K has been developed and applied to the reaction NO + 03 ->N0
2
+ 0
2
.
The activation energy for this reaction was found to vary by ~650 calories between 200 and 350 K. The best expression for fitting both the rate constants and the activation energies was found to be k = 9.43 x 10 -19 T 219 exp[-(764/T) cm 3 molec -I s -1 .
It has been found that singlet-oxygen 2( 1 ▲g, 1
 g) is produced in the reaction between Cl0
3
although probably not of significance in the stratosphere, this reaction is frequently used to generate C10 radicals for kinetic studies. In such studies, singlet oxygen can react with 0
3
to produce 0 atoms. The singlet oxygen produced in the reaction between Cl and 0
3
is a possible explanation for the 02-quenching effect on the quantum yield for ozone destruction in the photolysis Of C12/03/02 mixtures, an effect first discovered in 1934 by Norrish and Neville.
-14-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
The kinetics of chemiluminescence associated with the reactions of chlorine atoms with C1
2
0, C10
2
, and 0
3
have been investigated. In all three reactions the chemiluminescence could be attributed to the B 3 π(0 u
+ ) X l

+ g
transition of C1
2
.
For the Cl + C1
2
0 reaction the emission is totally attributed to the formation of excited state C1 of Cl with C10
2 excited state C1
2
2
in the disproportionation reaction of C10. The reactions
and 0
3
are more complicated. The Cl + C10
2
directly, or alternatively, C10
2
reaction may form
may serve as a good chaperon in the recombination of Cl to form C1
2
(B). The kinetic behavior of the Cl + 0
2 reaction is best explained by a mechanism involving the chlorine peroxidedimer
(ClOCl) and 0
2
(l g
).
A new source for HOCI in which dilute chlorine gas in helium is bubbled through a suspension of CaC0
3
in water has been developed. The HOCI so produced, which has been found to be relatively free of C1
2
0 impurity, has been used in the measurement of the rate constant for the reaction of OH with HOCI, the product distribution for the reaction of Cl with HOC1, and the UV absorption cross section of HOC1.
The reaction rate constant for OH + HOC1 was measured to be (1.8 ± 1.3) x 10 -13 cm 3 molec -I s -I at 298 K, which indicates that this reaction does not contribute significantly to loss of-stratospheric OH or HOC1. The primary products of Cl +
NOC1 were determined to be C1
7
and OH (91 ± 6%) at 298 K. Although the measured
HOCI cross sections are considerably different from previously recommended values, cancelling effects cause the calculated stratospheric photolysis rates for HOC1 below 35 km to be only slightly different from those currently used models.
The rate constant for the reaction 0 + N0
2
 0
2
+ NO has been measured by the discharge flow technique with chemiluminescence detection of the loss of 0 atoms. At 298 K the rate constant is 1.0 x 10 -11 cm 3 molec -l s -1 , in good agreement with the previous results. In the same experiments the rate constant for the reaction 0 + C10  C1 + 0
2 has also been measured. The rate constant for this reaction was measured to be (3.5 ± 0.16) x 10 -11 cm 3 molec -1 s -1 at 298 K.
Drs. J. P. BURROWS and R. A. COX -- Atomic Energy
Research Establishment,Harwell, England -- 80-334. 1R Laser Investigation of Halogen Species (completed).
_15-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
In this investigation infrared diode laser spectroscopy was used to determine the products formed in the reaction of C10 with N0
2
. Chlorine nitrate, ClONO
2
, is the only stable end product of this reaction at room temperature. These measurements gave a value of (1.8 ± 0.4) x 10 -31 cm 6 molec -2 s -1 for the reaction
C10 + N0
2
+ M  ClON0
2
+ M at 295 K and an upper limit of 5 ms for the lifetime of any isomeric products at this temperature.
Dr. R. A. COX -- Atomic Energy Research Establishment, Harwell, England
-- 82-400. IR Diode Laser Study of the Chemistry of Halogen Species
(completed).
This study confirmed the conclusion of the previous project 80-334 that, at laboratory temperatures and pressures, the chlorine nitrate molecule, ClONO
2
, is the only stable product of the reaction C10 + N0
2
+ M. The apparent rate of reaction decreases at high OC10 concentrations.
The photolysis products from OC10 were studied by UV absorption spectroscopy.
Dr. R. A. COX -- Atomic Energy Research Establishment, Harwell, England
-- 83-483. Halogen Species Chemistry by IR and UV Spectroscopy.
The kinetics of the reaction C1 + H0
2
has been studied over a range of pressures and temperatures. The major product channel gave HC1 + 0
2
. The ultraviolet absorption cross section for chlorine nitrate has been measured in the range 200-400 nm, and some preliminary kinetic studies of reactions involving chlorine nitrate with HC1, HBr, and H
2
have been made.
Drs. D. E. FREEMAN, K. YOSHINO, and W. H. PARKINSON -Harvard University
-- 82-412, 83-486. Photoabsorption Cross Section Of 02 in the 197-240 nm
Region.
Measurements of the Herzberg continuum cross section of 0
2
in the 193.5-204.0 nm region have been made. The measurements confirm values derived from recent data from balloonborne instruments for the 193.5-204 nm region, and preliminary analysis of the laboratory data for the 204-240 nm region yields values consistent with the in situ data. These new values of the Herzberg continuum cross section are considerably
-16-

I
Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms smaller than previously measured values that had been accepted for use in photochemical models.
Dr. C. J. HOWARD -- National Oceanic and Atmospheric Administration, Boulder --
76-100. Laser Magnetic Resonance Study of H0
2
Chemistry (completed).
H0
2
reactions of stratospheric importance were measured using a laser magnetic resonance technique. The rate constant for the reaction H0
2
+ N0
2
+.M - HOON0
M is 1.5 to 2.0 x 10 -31 cm6molec -2 s -1 . The major pathway is the production of
2
+ peroxynitric acid, a species not previously considered in the models.
The rate constant for the reaction H0
2
+ NO - N0
2
+ OH is 8 ± 2 x 10 -12 cm 3 molec -l s -I at room temperature, a value about 30 times faster than the previously accepted value. The temperature dependence of this reaction has been measured.
The rate constant for the reaction between H0
2
and 0
3
is 1.4 x 10 -14 exp(-580/T) cm 3 molec -l s -1 .
The reactions of HO and H0
2
with N
2
0
5 not important in the atmosphere.
appear to be very slow and consequently
Dr. C. J. HOWARD -- National Oceanic and Atmospheric Administration, Boulder --
77-223. Study of C10 Chemistry by Laser Magnetic Resonance (completed).
The far-infrared Zeeman spectrum of C10 has been observed and analyzed. Five observed transitions of wavelengths between 444 and 713 pm have been compared with values predicted with spectroscopic constants from the literature. These measurements provide the basis for Laser Magnetic Resonance detection of C10 radicals.
The rate constant for the reaction H02 + Clo was measured over the temperature range 235-393 K. The result does not fit a normal Arrhenius expression, k = 3.3 x 10 -11 exp  -850/T] + 4.5 x 10 -12 (T/300 )-3.7
cm 3 molec -l s -1 . At temperatures below room temperature the reaction has negative temperature dependence.
The temperature dependence of the reaction of C10 with NO has been investigated. The results are k = (7.1 ± 1.4) x
-17

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
10 -12 exp[(270 ± 50)/T] cm3molec -l s -l for the range 202 to 393 K. These data are in good agreement with other direct studies.
The C10 + N0
2
+ M recombination reaction has been studied as a function of temperature and in three different gases, He, 0
2
, and N
2
. The results are k(M =
He, T = 250-387 K) (2.8 ± 0.6) x 10 -33 exp[(1090 ± 80)/T], k(M+= 0
2
, T =
250-416 K)(3.5 ± 0.6) x 1033 exp[(1180 - 80)/T], and k(M = N
2
, T297 K) = (2.09
± 0.3) x 10 -31 cm 6 molec -2 s -l . This was the first measurement of this reaction in oxygen. Theother results agree with previous studies.
Dr. C. J. HOWARD -- National Oceanic and Atmospheric Administration,
Boulder -- 79-289, 82-424. Kinetic Studies of Stratospheric Chlorine
Chemistry.
A trace gas detection system using a tunable infrared diode laser and a multipass absorption cell has been assembled. This system was used to measure the concentration of N
2
0 in air, 0.298 ± 0.005 ppmv. This result indicates that there is an error in the calibration standards used by some measurement groups.
The heat of formation of H0
2
radicals was determined by measuring the rate constants in the forward and reverse directions for the eqVilibrium. reactions:
H0
2
+ NO = OH + N0
2
. The value, ▲H f298
= 2.5 ± 0.6 kcal mol revises the previous recommendation, 0.5 kcal mol -1 .
-1 , significantly
The rate constants and branching ratio for the reaction of H0
2
and Cl radicals have been measured as a function of temperature. A new product path OH + C10
(b) is observed in addition to the previously accepted path HC1 + 0
2 k a
= (1.8 ± 0.5) x 10 -11 exp[(170 ± 80)/T] cm 3 molec -l s -l . and k b
(a
= (4.1 ± 0.8) x
10 -l1 exp[-(450 ± 60)/T1 cm 3 molec -l s -l . The total rate constant k(4.2 ± 0.7) x
10 -1l is independent of temperature for T= 250-420 K. This value is in reasonable agreement with the average of all previous measurements, which were all made at room temperature and cover a range of about a factor of four.
The temperature dependence of the rate constant for the reaction OH + HN0
3 been measured in a discharge flow system. The results indicated that the
has reaction has a
-18-

I
Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms strong negative temperature dependence below room temperature, k = (2.0 ± 0.4) x 10 -l4 exp [(430 ± 60)/T] cm 3 molec -l S -l . Between room temperature and 400 K the rate constant changes only slightly, with measured values falling between 7 and
9 times 10 -l4 . Although these results are similar to some other studies, they do not agree well with them. No satisfactory explanation for the differences has been found. A study of the products of the OH + HN0
3
reaction indicated N0
3
and
H20 are dominant.
The rate constant for the H0
2
+ HO reaction is 2.0 ± 0.6 x 10 -l3 exp[(595 ±
120)/T] cm 3 molec -l s -l between 253 and 390 K, and that for the reaction OH + C10 is 8.0 ± 1.4 x 10 -l2 exp[(235 ± 46)/T1] cm 3 molec -l s -l between 219 and 373 K. The branching ratio k a
/(k a
+ kb) for the products (a) H0
2
+ Cl and (b) HU + 0
2
is
0.86 ± 0.14 for the reaction of OH with Cl0.
The rate constant for the N0
3
+ NO reaction is (1.55 ± 0.3) x 10 -1l exp [ N195 ±
SO/)T] cm 3 molec -l s -l for temperatures lower than 300K. For temperatures above 300
K the value is 2.9 x 10 -l cm 3 molec -l s -l and shows very little change with temperature.
Dr. M. J. KURYLO National Bureau of Standards ---
78-233. Rates of Reaction of Cl Atoms with the Primary
Products of Alkane Photooxidation (completed).
Flash photolysis resonance fluorescence (FPRF) has been used to establish a limiting rate constant for the reaction of Cl with OCS (K≤1 x 10 -13 cm 3 molec -l s -l ; 220-323 K). Similarly the rate constant for the reaction Cl + H
2
CO has been measured as (1.09 ± 0.40) x 10 -l0 exp[-131 ± 98)/T] cm 3 molec -l s -l over the temperature range 223 to 323 K. In other FPRF experiments the rate constant for
OH + CH
3
CC1 was found to be (5.41 ± 1-8) x 10 -l2 exp[(1810 ± 100)/T m 3 molec -l s -l
(253-363 K). This markedly lower value leads to revised model calculations Of
CH
3
CC1
3
tropospheric lifetimes and then to the prediction of higher tropospheric
OH concentrations. An upper limit to the rate constant for the reaction CH3 +
0
2
OH + H
2
CO has been set at 3 x 10 -l6 cm 3 molec -l s -l at 368 K based on the sensitivity of monitoring the OH product by resonance fluorescence. The temperature dependence of the rate constant for the ozone formation reaction
0 + 0
2
+ M (M = N
2
, 0
2
, Ar), which has been measured by FPRF, provides the first detailed analysis for M = N
2
_19-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms and 0
2
and indicates a weaker temperature dependence than previously assumed for M = 0
2
. The recommended valuf1for+ ozone formation in air [(6.3 ± 0.9) x
10 -34 (T/300)-9 - 0.5) cm 6 molec -2 s13 is in good agreement with current NASA recommendations. Studies of the atmospheric quenching Of 0
2
( that vibrational deactivation dominates over reaction with 0
3
1 ▲,v > 0) indicate
Other experiments indicated an upper limit of 15% on the production of 0
2
O( l D) with 0
3
.
(l

) by the reaction of
Dr. M. J. KURYLO -- National Bureau of Standards -- 80-307. Reactions within the HO
X
Cycle (completed).
A steady-state photolysis experiment utilizing mass spectrometric detection was used to investigate the reaction H 18 0 + H0
2
. The result do not support the existences of a linear adduct reaction intermediate as suggested by the proposed pressure dependence of the reaction. Modeling analysis of the experiments best duplicates the product observations for rate constant values
(OH + H0
2
) in the range 1-2 x 10 -l0 cm temperature dependence of the OH + H
2
3
0 molec
2
-l s -l at atmospheric pressure. The
reaction was determined by FPRF over the temperature range 250-370 K, resulting in a recommended value of (2.91 ± 0.30) x10 -l2 exp[-(161 ± 32)/T] cm 3 molec -l s -l . Computer simulations of this and other investigations indicate significant problems in the pre-1980 studies of the
OH + H
2
0
2
reaction. Experimental modifications to an existing kinetic spectroscopy apparatus are being made to permit measurement of the H0
2
self reaction.
This work is being continued under project 82-402.
Drs. M. J. KURYLO and A. H. LAUFER -- National Bureau of Standards --
82-402. Reactions within the HOXI N0 x
, ClO x
, and SO x
Cycles.
Rate constants for the reaction between C1 atoms and HON02 were measured by
FPRF between 243 and 298 K. The data can be fit to the Arrhenius expression 5.1 x 10 -l2 exp(-1700/T) cm 3 molec -l s -l , indicating the lack of any importance of the reaction in stratospheric C1 removal. A reinvestigation of the C1 atom reaction with chlorine nitrate by FPRF over the temperature range 220-296 K yielded the rate constant expression 7.3 x 10 -12 exp(165/T) cm 3 molec -l s -l . These results supersede earlier measurements from
_20-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms this laboratory, which are thought to have been complicated by 0 atom interference. The rate constants for the reactions of C1 and OH with CH
3
CN have been measured by FPRF. At room temperature an upper limit for the rate constant of the reaction between C1 and CHICN is 2 x 10 -l5 cm 3 molec -l S -l . The temperature dependence between 250 and 363 K for the rate constant of the OH + CH
3
CN reaction
Is6.28 x10 -13 (-1030/T)cm 3 mo1ec -l s -l .
The rate constants for the HOI + H0
2
+ M and H0
2
+ N0
2
+ M reactions have been determined by flash photolysis kinetic absorption spectroscopy. In the presence of N
2
and 0
2
as third bodies the rate constants for the H0
2
+ H0
2
+ M reactions are, respectively, 5.95 x 10 -32 cm 6 molec -4 s -I and 4.53 x 10 -32 cm 6 molec -4 s -1 . Likewise for the H0
2
+ N0
2
+ M reaction, the values using N
2
and 0
2 as, third bodies are, respectively, 1.5 x 10 -32 cm 6 molec -2 S -1 and 1.3 x 10 -31 cm 6 molec -2 S .
Dr. G. LE BRAS -- Centre de Recherches sur la Chimi de la Combustion et des
Hautes Temperatures, CNRS, Orleans, France -- 83-488. Study of OH + ClO.
Kinetics parameters, rate constant, and branching ratio of the reaction
OH + C10  H0
2
+ C1 (la)
 HC1 + 0
2
(lb) have been studied in a discharge flow reactor at 298 K and 1 torr. The final data are k
1
= 1.94 ± 0.18 x 10 -11 cm 3 molec -1 s -1 and k la
/k l
= 0.98 ± 0.07.
Reactions of N
2
0
5
with C10, OH, and H0
2
.
This study is just getting started.
Dr. G. LE BRAS -- Centre de Recherches sur la Chimie de la Combustion et des
Hautes Temperatures, CNRS, Orleans, France -- 85-545. Kinetic Study of the
Dr. Y. P. LEE-- Tsing-Hua University, Taiwan -- 83-480.
Product Determination of Atmospheric Reactions.
The matrix isolation technique is being combined with a discharge-flow system to determine the products of some important stratospheric reactions. The matrix-isolated products will be analyzed by infrared absorption spectroscopy

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
The technique will be applied to the reactions OH + N0
2
+ M, OH + C10, and H0
2
+ C10.
Dr. J. N. PITTS, JR. -- University of California at Riverside -- 74-2.
Atmospheric Reactions of Fluorocarbons (completed).
Reaction rate constants have been measured for the reactions of 0('D) with CFCs
11, 12, 22, 113, and 114 and of OH with CFCs 11, 12, and 22. The results-indicate that in the stratosphere the reaction of O( l D) atoms with CFCs
11 and 12 is secondary to photolysis, whereas the reaction of 0H with CFC 22 is much more important than photolysis. The photooxidation products of 11, 12, and
22 at 184.9 nm, i.e., COFC1 and COF
2
as appropriate, are also observed to be the products for reaction with O( l D).
Dr. J. N. PITTS, JR. -- University of California at Riverside ---77-190.
Atmospheric Chemistry of Peroxynitric Acid (completed).
The HO
2
NO
2
cross sections vary smoothly from 1.6 x 10 -17 cm 2 molec -1 at 190 nm to
 2 x 10 -20 cm 2 molec -1 at 330 nm. The infrared cross sections for the 802.7 and
1303.9 cm -1 Q branches of H0
2
NO
2
at 0.06 cm -1 resolution are 2.1 x 10 -19 and
1.8 x 10 -18 cm 2 molec -1 , respectively.
Dr. A. R. RAVISHANKARA -- Georgia Institute of
Technology -- 80-295. A Study of the Reaction of OH with C10 (completed).
The overall rate of the reaction OH + C10 has been measured in a discharge flow system by resonance fluorescence detection of OH: k = (1.17 ± 0.33) x 10 -11 cm 3 molec -l s -1 nearly independent of temperature for 248 < T < 335 K. This result includes a correction for the reaction of product H0
2
with Cl, which produces
OH and is responsible for an earlier underestimation of the rate constant.
Attempts to develop a microwave interferometry system to measure the yield of
HC1 in this reaction proved unsuccessful because of difficulty in generating an adequate 625 GHz signal.
Dr. A. R. RAVISHANKARA -- 'Georgia Institute of Technology -- 81-368,
83-449; Drs. A. R. RAVISHANKARA and P. H. WINE -- Georgia Institute of
Technology -84-499. Laboratory Studies of Stratospheric Reactions.
-22-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
Several reactions-important in stratospheric modeling calculations were investigated. The rate constants for the reactions N0
3
+ NO  2NO
2
, N0
3
+ N0
2
 N
2
0
5
, Clo + 0( 3 p)  Cl + 0
2
, and C1
2
+ 0( 3 p) products were determined. The results indicate that some of the previously accepted kinetic parameters for these reactions may need to be revised. Significant new kinetic data have been obtained for the reactions of chlorine species with O( I D). Aspects of the photochemistry of N
2 of NO
3
O
5
have been investigated, and new absorption cross sections
have been determined.
Drs. J. A. SILVER, M. S. ZAHNISER, and C. E. KOLB -Aerodyne Research,
Inc. -- 82-401, 84-494. A Study of the Gas Phase Reaction of Sodium
Hydroxide with Hydrochloric Acid.
This project explores the potential role of meteoritic sodium in stratospheric chemistry by examining a reaction that could couple sodium chemistry with chlorine chemistry. The rate constant for the gas-phase reaction of NaOH with
HC1 is 2.8 ± 0.9 x 10 -10 cm3molec-ls-1. Work is in progress toward measuring the rate constant for the reaction between Na0
2 cross sections of NaCl.
and HC1 and the photodissociation
Dr. T. C. STEIMLE -- University of Oregon -- 82-418. Identification of
Photodissociation Products by Resonance-Enhanced Multiphoton Ionization
(completed).
In a first effort to identify the products of the photodissociation of peroxynitric acid, H0
2
NO
2
, the compound was photolyzed in a flow system with UV at 193, 248, and 308 nm. The principal nitrogen-containing product, detected by laserinduced fluorescence approximately I s after photolysis, was N0
2
. Its high quantum yield suggested that as yet unidentified secondary reactions contributed to its formation.
Dr. T. C. STEIMLE -- University of Oregon -- 84-509.
Absorption Cross Section of H0
2
NO
2
.
Pernitric acid is believed to play an important role in stratospheric chemistry, and more precise measurements of its UV cross sections are needed.
In this study, laser techniques will be employed for generation of incident UV over the 260-310 nm range as well as for monitoring H0
2
NO
2
in the infrared.
-23-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
Dr. F. STUHL -- University of Bochum -- 77-170. Determination of the Photodissociation Process and Absorption Cross
Section of FC-11 and 12 in the Near UV (completed).
The absorption spectra of some chlorine-containing methanes (CC14 CHC13,
CH2C12, CFC 13, and CFC 31) and ethanes (CFC 113,FC 114, CFC 115, CFC 133a, and
CFC 142b) and also of N
2
0 were determined at wavelengths around 220 nm. Some of these spectra were obtained at both 298 and 208 K. A chemical method was used to determine the absorption cross section of CFC 11 at 253.7 nm and the absorption properties at wavelengths greater than 280 nm. It is concluded from these experiments that the tropospheric decay rate of CFC 11 is smaller than 10-10 s-1 for homogeneous gas phase photolysis.
Dr. G. A. TAKACS -- Rochester Institute of Technology
-- 77-196. Photcabsorption Cross Sections for Compounds of Atmospheric Interest (completed).
Ultraviolet-visible absorption spectra have been measured and solar photodissociation rates have been calculated for S0
2
C1
2
, CC1
3
NO
2
, CF
3
NOC1, SOC1
2
,
S0
2
F
2
, S0
2
ClF, CH
3
SO
2
Cl, and CC1
3
SCIA maximum photoabsorption cross section, which indicates a long stratospheric lifetime, has been established for
HC10
4
. Attempts to measure photoabsorption spectra for gaseous ONO(SO
2
)OH and
ONO(SO
2
)Cl were unsuccessful. Photolysis of CFC 11 and CC1
4
in the presence of solid NaCl with wavelengths lon er than 300 nm results in maximums of 2.3 x 10 -4 and 2.4 x 10 -1 molec, respectively, photodissociating per incident photon on the
NaCl.
Dr. B. A. THRUSH -- University of Cambridge -- 75-58,
75-58-11. Reactions of the H0
2
Radical Studied by Laser
Magnetic Resonance (completed).
The rate coefficient of the reaction 0 + H0
2
was measured for the first time.
The value found, 3.5 ± 1.0 x 10 -11 cm 3 molec -l s -l at 293 K, improves the fit of the calculated OH profile with Anderson's recent measurements. The rate coefficient of the reaction OH + H0
2
was measured based on direct measurement_of,H0
2 and found to be 5.1± 1.6 x 10 -11 cm 3 molec -l s -l at 293 K.
Dr. B. A. THRUSH -- University of Cambridge -- 81-378.
Reactions of H0
2
Radicals Studied by Mid Infrared Laser
Magnetic Resonance Spectroscopy (completed).

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
Laser magnetic resonance in the mid infrared was used to detect H0
2
in a flow system. Preliminary measurements of the rate coefficient of the reaction H02 +
NO - HO + N0
2
gave a value of 7 x 10 -12 cm 3 molec -l s -1 at 10 torr total pressure.
Dr. J. WIESENFELD -- Cornell University -- 76-128,
77-220. Photochemistry of Small Chlorinated Molecules
(completed).
The photochemistry of chlorine nitrate was studied by determining the yields of
Cl and C10 from the flash photolysis of ClONO
2
. The rate of reaction between 0 and ClON0
2
has been measured and is in good agreement with the literature value.
Dr. R. ZELLNER -- University of Goettingen, F.R.G. -77-195.
Experimental Investigation of the Branching
Ratio in the O( l D) + H
2
0 Reaction (completed).
The branching ratio in the reaction O( l D) + H
2
0  2 HO (1) and  H
2
+ 0
2
(1') has been determined at 298 K from direct measurements of HO and H
2
to be 0.01
(K l
'/K i
) (+0.005, -0.01). The main conclusions to be drawn from this result are:
1. Reaction l' is not an important source of H
2 mesosphere.
in the upper stratosphere and
2. The reduction of mesospheric HO x
through the occurrence of reaction l' is not large enough to account for discrepancies in calculated and measured
0
3
concentrations.
DR. R. ZELLNER -- University of Goettingen, F.R.G. -
80-331.Kinetic Investigations of the-Reaction Cla + 0
2
( 1 ▲ ). Products and the Equilibrium Constant for the Possible Complex Formation C10 + 0
2

OC10
2
(completed).
The reaction between C10 and 0
2
( 1 ▲ ), possibly forming C10
3
, is too slow to be a significant scavenging process for C10. The reaction between C10 and 0
2
(3

) is also found to be slow, (K~l x l0 -17 cm 3 s -1 ). Its equilibrium constant however is
 5x10 -20 cm 3 molec -1 at 298 K, indicating possible importance at stratospheric temperatures.
DR. R. ZELLNER -- University of Goettingen, F.R.G. -83-478.
Laboratory Studies of Atmospheric RadicalRadical and
Photochemical Reactions Using Laser Photolysis/Laser
Line Spectrometry.
-25-

Table 3 (continued)
Investigation of Reaction Rates, Products, and Mechanisms
The reaction of C10 with 0 is being reinvestigated with emphasis on the possible effect of 0
2
on the rate constant. This involves a refined determination of the _equilibrium constant of C10 + On  C10 0
2
over a wider temperature range. Preliminary results do not support a strong 0
2
effect on any C10 rate constant.
In another experiment the reaction ClONO
2
+ HC1 is being studied under wall-free conditions. The ClON0
2
is produced in situ by photolysis of C10
2 in the presence ot N0
2
and defined concentrations of HC1. UV absorption spectroscopy is used to monitor the buildup and consumption of ClON09.
B. Source and Sink Studies
Dr. P. AUSLOOS -- National Bureau of Standards -- 77-186,
78-254. Follow up for Photodecomposition of Chloromethanes
Absorbed on Silica Surfaces (completed).
The decomposition of CF
2
C1
2
, CFC1
3
, CH
3
CI, CC1
4
, CH
3
CC1
3
, and CH
2
CC1
2
on
Tunisian sand at dilute concentrations (100 ppb - 100 ppm) has been investigated in both the presence and the absence of light and/or moisture.
Experiments with 13 CC14, that one molecule of 13 C0 the surface. For CH
3
CC1
3
13 CFC1
3
, and 13 CF
2
C1
2
in the presence of oxygen show
2
is produced per halomethane molecule destroyed on
, surface destruction leads to CH
2
CC1
2
rather than C0
2
.
Under all conditions relative stabilities were as follows CF
2
C1
2
> CFC1
3
> CC1
4
> CH
3
CC1
3
. Both with and without light the rate of surface-induced-destruction decreases rapidly with increasing moisture content. When the chlorofluoromethanes were exposed to sand with a moisture content in equilibrium with laboratory air (35% humidity at 20 0 C), no decomposition was observed. However, a sudden reduction in moisture content by 40% or more leads to a measurable destruction rate for CC1
4 and CH
3
CC1
3
.
Dr. J. W. BIRKS -- University of Illinois -- 76-117B.
Studies of Heterogeneous Reactions (completed).
See Table 3, Section A.
-26-

Dr. F. BRUNER -- Urbino University, Italy -- 80-330. Atmospheric
Monitoring of F-21 (completed).
Table 3 (continued)
Source and Sink Studies-
The occurrence of CFC 21 suggests the existence of a CFC 11 sink by desert destruction. Two intercalibrated measurement stations capable of detecting the absolute difference in mean daily CFC 11 concentration and the possible simultaneous occurrence of CFC 21 were arranged in a desert region about 500 km apart and oriented along the direction of the prevailing winds -- the upwind station located along the edge of the desert, the downwind station situated in the desert. A sampling campaign at the two stations was carried out during two weeks of favorable winds during May, 1982. The samples collected were analyzed for CFC 11 and 21 by a GCMS procedure. The results show a negligible amount of
CFC 21 at both stations but a constant, higher concentration of CFC 11 at the up-wind station. The data were submitted to a statistical procedure to evaluate a possible desert destruction effect for CFC 11 and found to be insufficient to assess the effect.
Dr. M. J. CAMPBELL -- Washington State University -75-53.
Chlorofluoromethane Destruction by Natural Ionization (completed).
Laboratory measurements at high irradiation levels show large rate constants for removal Of CC14 and CFC 11. The rate constant for CFC 12 is much smaller.
The significance of these results with respect to atmosphere sinks for the CFCs is questionable.
Drs. D. M. CUNNOLD, F. N. ALYEA, and R. G. PRINN -- CAP Incorporated --
77-213, 78-251, 79-281, 80-323, 81-361, 82-422, 83-476. Coordination and
Analysis of Data for the Atmospheric Lifetime Experiment (ALE).
CAP is continuing its work on the processing of the raw atmospheric and calibration tank chromatographic analyses received in digital form from ERT.
This process includes computation of calibrated atmospheric concentration from the raw data, statistical analyses of the raw and calibrated data, determination of trends in the observed species, and reporting of the calibrated data in graphical and tabular forms.
-27-

Table 3 (continued)
Source and Sink Studies
CAP is also using its optimal estimation technique to compute atmospheric lifetimes of CFC 11, CFC 12, methyl chloroform, and carbon tetrachloride from the observed trends in the species.
The three year data set suggests that if any tropospheric sink for CFCs exists it must be very small. If it is assumed to be negligible and the photochemical lifetimes are taken for the species, it is possible to "run ALE in reverse" and hence calculate the trend in release rates for the various species. For CFC 12 the derived releases are significantly higher than the current FPP estimates.
See Lovelock and Simmonds, 77-193, et al., Rasmussen, 77-201, et al., and Rosen, 81-377.
Dr. R. J. DONOVAN -- University of. Edinburgh, Scotland -- 79-286. Reaction of C10 with OH: A Potential Sink for ClO x
(completed).
The reaction between OH and C10 was studied at room temperature using flash photolysis. At a total reassure of 12 torr the rate coefficient is (3.3 ± 0.7) x
10 -12 cm 3 molec -l s -1 and the reaction rate increases with pressure.
Dr. P. J. B. FRASER -- Commonwealth Scientific and Industrial Research
Organization (CSIRO), Aspendale, Australia -- 82-415. Atmospheric Lifetime
Experiment Participant (completed).
The contract enabled Dr. Fraser to attend ALE data analysis meetings in the USA and UK during the period November, 1982, to April, 1984. It also assisted the continuing collaboration of the Australian Baseline Station in the global CFC monitoring network.
Dr. P. J. B. FRASER -- Commonwealth Scientific and Industrial Research
Organization (CSIRO), Aspendale, Australia -- 85-540. Global Atmospheric
Gases Experiment (GAGE).
The contract provides supplemental travel funds to enable the investigator to participate in the 1985 GAGE meetings.
-28-

Table 3 (continued)
Source and Sink Studies
Dr. M. KAUFMAN -- Emory University -- 76-126, 77-197. Studies of Compounds of Sulfur, oxygen, and Chlorine (completed).
The three body recombination rate constant for Cl and S0
2
at 295 K has been found to be 1.3 x 10 -33 cm 6 molec -2 s -1 with Ar, 2.3 x 10 -33 cm 6 molec -2 s -1 with N2, and 19 x
10 -33 cm 6 molec -2 s -1 with S0
2
. At 281 K the first and third values become 2.9 x 10 -33 and 20 x 10 -33 , respectively. Ultraviolet cross sections of S02CI2 and HOS0
2
C1 have been determined, and the incorporation of 36C1 into sulfate-type aerosol particles has been studied. Surface effects appear to have dominated the latter experiment.
When OCS is added to a Cl/C1
2
/Ar mixture at room temperature,SC1+and SC11 ions are detected mass spectrometrically. The rate constant for the reaction
Cl + OCSSC1 + CO is less than 10 -16 cm 3 molec -l s -1 at 296 K.
Dr. F. KORTE -- Technical University of Munich, F.R.G. -- 77-194.
Photodegradation of Chlorofluoromethanes in the Troposphere (completed).
The photodegradataion of CFC 11 and CFC 12 on silica gel and on Mecca sand was studied with the aid of 14 C-labelled compounds. Whereas in the dark no change was determined with silica gel, there was significant decomposition on the sand with formation of 14CO
2
(up to 50%). Irradiation with UV ( >290 nm) led to 1-5% decomposition of the CFCs on silica gel also with formation of 14 CO
2
. Irradiation with UV was not observed to increase the decomposition rate on sand. The results suggest that decomposition takes place at active sites on the surface.
Dr. M. J. KURYLO -- National Bureau of Standards -78-233. Rates of Reaction of Cl Atoms with the Primary Products of Alkane Photooxidation (completed).
See Table 3, Section A.
Dr. J. E. LOVELOCK -- University of Reading -- 75-67,
77-144. Unidentified Factors in the Fluorocarbon-Ozone
Problem (completed).
Coarse Saharan surface dust showed an unusual degree of retention for CFC 11 and
CC14- Investigations were made on the
-29-

Table 3 (continued)
Source and Sink Studies relationship between photochemically produced atmospheric peroxy compounds
(e.g., peroxyacetyl nitrate) and the incidence of skin carcinoma.
Observations on dissolved gases in the ocean were made during the April 1977 voyage of RRS Challenger. Concentrations of N
2
0 in ocean and atmosphere confirmed earlier estimates of N
2
0 flux from the ocean.
Drs. J. E. LOVELOCK and P. G. SIMMONDS -- Private -77-193, 78-243,
79-280, 80-324, 81-370, 82-421. Operation of Stations in Adrigole and
Barbados for the Atmospheric Lifetime Experiment (completed).
Automated long-term ground measurement stations have been operated in Adrigole
(continuing the data base already collected there) and in Barbados.
Hewlett-Packard electroncapture gas chromatographs were used to collect data for CFCs 11, 12, and 113, CH
3
CC1
3
, CC1
4
, and N
2
0, which were processed, tabulated, and forwarded to CAP Associates for analysis.
Both stations operated well with data being processed from March 3, 1978,
(Adrigole) and July 12, 1978, (Barbados) up to December 31, 1983. The Adrigole station has been shut down, but the Barbados station continues as part of the
GAGE network (see also Simmonds, 84-515).
Dr. L. R. MARTIN -- Aerospace Corp. -- 75-81, 75-81-11. Laboratory
Investigation of the Heterogeneous Interaction of Cl and C10 with H
2
SO
4
(completed).
A flowing afterglow apparatus was used to measure the rate of the heterogeneous reactions of Cl and CIO with sulfuric acid, simulating the stratospheric aerosol. The reaction rate of Cl is too slow for its reaction to constitute a significant sink, although rates were markedly increased by the presence of certain metal salts in the sulfuric acid. Even at strato spheric temperatures the HCl formed goes into the vapor phase. The for C10 on H
2
SO substrates is 1 x 10 -3 at room temperature. These, the first examples of
4
/H
2
O heterogeneous reactions with stratospheric aerosol, are not in any models.
Dr. V. A. MOHNEN -- State University of New York, Albany -- 75-64. Ion
Molecule Reactions Involving Fluorocarbons (completed).
-30-

Table 3 (continued)
Source and Sink Studies
Ion molecule reactions between the equilibrium ion distribution formed in pure air -like gas mixtures and CFC 12 were studied. From these investigations it was concluded that: (1) stable CFC 12 attachments -to ions ("cluster formation") of the form H + (H
2
0)n, 0
2
-.(H
2
0)n, C0
3
-(H
2
0)n, and C0
4
-(H
2 dissociative charge transfer reactions between H + -(H
2
0)n do not occur; (2)
0)n and CFC 12 are not, observed for all n > 2; (3) approximate rate constants for dissociative charge transfer reactions between CFC 12 and O
2
-. H
2
0 and CFC 12 and C0 are 3 x 10 -12 cm 3 s -l and <2 x 10 -13 cm s -1 , respectively; (4 knowledge of time integrated rate constants for atmospheric negative ions is necessary before the importance of ion reactions with CFCs can be estimated, but the likelihood of substantial importance is small.
Dr. L. F. PHILLIPS -- University of Canterbury, N.Z. 78-241.
Determination of Atomic Oxygen Yields in the Photolysis of HOC1 and C100
(completed).
The photolysis was studied by looking for prompt 0 atoms by observation of resonance fluorescence on a nanosecond time scale. Detection limits for ground-state oxygen atoms produced by photolysis of N0
2
were established.
Gaseous mixtures containing HOC1 were photolyzed with UV radiation at 337 nm from a nitrogen laser to determine whether the HOC1  HC1 + 0 reaction path occurred.
Because the signal to noise ratio was too low, attempts to measure oxygen atoms by resonance fluorescence gave inconclusive results. Recommendations were made for improving the sensitivity of the detection method in future studies.
Dr. L. F. PHILLIPS -- University of Canterbury, N.Z. -81-342. Yield of
Atomic Oxygen from HOCI Photolysis at 308 = (completed).
Although the major products from the ultraviolet photolysis of HOC1 were known to be Cl and OH, uncertainty remained about the extent of a second product channel yielding HC1 and 0. Equilibrium mixtures containing HOC1, C1
2
0, and H
2
0 were therefore photolyzed with a XeCl laser at 300 nm. No oxygen atoms were detected by resonance fluorescence, indicating that the quantum yield for this secondary channel was below 1% and thus not significant.
_31-

Table 3 (continued)
Source and Sink Studies
Dr. J. N. PITTS, JR. -- University of California at
Riverside -- 75-12. Monitoring and Atmospheric
Reactions of Fluorocarbons (completed).
CFCs 11 and 12 are photochemically stable in simulated sunlight, even when irradiated for several weeks. Plant tissues did not absorb measurable quantities of CFCs 11, 12, or 22, and no adverse effects could be measured.
CFCs penetrate into the soil atmosphere, and concentrations change in direct relationship with changes in concentration in the atmosphere above ground.
Dr. R. A. RASMUSSEN -- Washington State University --
75-71. Measurement of Fluorocarbon Content of "Antique"
Air Samples (completed).
A sensitive method for the determination of low parts per trillion analysis of
CFCs 11 and 12 in small-volume air samples in containers was developed and applied to a wide variety of vessels believed to contain antique air. All samples analyzed showed varying levels of CFCs. Contamination during handling is not a problem, so that either CFCs were present in nature prior to 1930 or the samples were contaminated by leakage during storage.
Dr. R. A. RASMUSSEN -- Rasmussen Associates -- 75-84.
Collection and Analysis of Antarctic Ice Cores
(completed).
The concentration of halocarbons in air obtained from Antarctic snow shows no enrichment in samples obtained from the Ross ice shelf (mainly -30 F), whereas there is enrichment in samples obtained from the South Pole (-50 to -60 F).
Dr. R. A. RASMUSSEN -- Private -- 76-140. Lower
Stratospheric Measurement of Non-methane Hydrocarbons
(completed).
Ethane, ethylene, and acetylene are found in the upper troposphere and lower stratosphere at concentrations of 40-820 ppt. Total concentrations of the three species range from 1085 ppt (NH troposphere) to 323 ppt (SH stratosphere).
-32-

Table 3 (continued)
Source and Sink Studies
Dr. R. A. RASMUSSEN -- Oregon Graduate Center --
77-201, 78-248, 78-263,.79-279, 80-325, 81-376. operation of Stations in
American Samoa, Cape Meares, Oregon, and Tasmania for the Atmospheric
Lifetime Experiment (completed).
Automated long-term ground measurement stations were operated in American Samoa and Tasmania as detailed in 77-193, et al. (Lovelock and Simmonds). Data have been processed from May, 1978, (Tasmania) and June, 1978, (American Samoa) up to
June, 1982.
The fifth ALE station at Cape Meares, Oregon, became operational early in 1980 and contributed measurement data routinely to the ALE network.
Propagation of the standards for the networks and their referencing back to OGC were part of the program.
The Tasmanian instrument has been moved into the Australian baseline station, and data have continued to be available to the ALE Team. The ALE 5840 and the
Australian 5880 instruments were intercompared to make the data consistent.
Dr. R. A. RASMUSSEN -- Oregon Graduate Center -
77-215. Kilauea Volcanic Emissions -- Halocarbon
Measurements (completed).
Electron capture gas chromatograph analyses were made on fumerolic emissions from two vents on Kilauea at the site of the September, 1977, lava flow. Some 20 halocarbons were observed and compared with local control samples. CFCs 11 and
12, CC14, and CH
3
CC1
3
were not significantly different from controls. Peaks tentatively identified as N
2
0 and methyl halides showed elevated concentrations versus controls. The presence of N
2
0 was confirmed by GCMS.
Dr. R. A. RASMUSSEN -- Oregon Graduate Center -- 82-416.
CFC 11 Release Rate from Rigid Polyurethane Foams.
The rate of release of CFC 11 from rigid polyurethane foams by monitoring the fluorocarbon level in the purge gases from environmental chambers containing samples of PUR boardstock has been determined. The results indicate that the half-life of chorofluorocarbon in undisturbed closed-cell foams can exceed 100 years. Actual residence be determined
-33-

Table 3 (continued)
Source and Sink Studies by the service life of the freezer, vehicle, building, or other structure insulated with such foams and will thus be limited to a few decades.
Dr. R. D. ROSEN -- ERT, Inc. -- 81-377. Data Processing for the
Atmospheric Lifetime Experiment (ALE) (completed) .
The data from the five automated long term ground measurement stations [cf.
77-193, et al. (Lovelock and Simmonds), and 81-376 (Rasmussen)] are received, archived, verified, and converted onto disc storage for transmission to CAP
Inc. This contract terminated on March 14, 1982, when Rosen left ERT and joined
Atmospheric and Environmental Research, Inc. (AER). The work continued under a
NASA contract as part of the NASA-CMA FPP cofunded Atmospheric Lifetime
Experiment. See Simmonds, 84-515.
Dr. C. SANDORFY -- University of Montreal -- 73-2.
Spectroscopy and Photochemical Changes of
Fluorocarbons (completed).
The vacuum ultraviolet and photoelectron spectra of CFCs were measured. The photochemical vulnerability of these molecules was predicted from their spectra.
R. E. SHAMEL -- A. D. Little, Inc. -- 79-275.
Analysis of Release of FC-11 from Rigid Plastic
Foam Products in the U. S. (completed) -
The lifetime for CFC 11 emissions from rigid foam is much longer than previously assumed and will not be a problem for the ALE lifetime calculations.
Dr. P. G. SIMMONDS -- Private -- 84-515.
Global Atmospheric Gases Experiment
(GAGE), Barbados Station.
The Barbados station, which with other former Atmospheric Lifetime Experiment
(ALE) stations now forms part of the GAGE network, is being supported.
Drs. P. G. SIMMONDS and J. E. LOVELOCK -- Private -79-269.
See Table 3, Section C.
Determination of Tropospheric Halocarbons and Their Relative
Importance (completed).
-34-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Dr. J. BALLARD -- Rutherford Appleton Laboratory, England -- 82-444.
Laboratory Spectroscopic Studies of Stratospheric Gases (completed).
A very long path (1 km) coolable absorption cell (white cell) was built and linked to a high resolution interFe-rometer. The system was used to investigate the spectrum (0.004 cm -1 ) of C0
2
. Shorter cells were used to investigate the spectrum of N0
2
, to measure the temperature dependence of the strength and pressure broadened widths of spectral lines for HC1
(3-5 ), and to assess interferences from H stratospheric determination of HF.
2
O, CH
4
, and N
2
O in the
Dr. J. W. BIRKS; Drs. C. J. HOWARD and F. C. FEHSENFELD
-- University of Colorado; National Oceanic-and
Atmospheric Administration, Boulder -- 77-222. Development of a Technique for Measuring the Total Chlorine Content in Air
(completed) .
The goal of this project was to develop an analytical instrument for measuring the total chlorine content of air. The technique developed did not have adequate sensitivity to analyze stratospheric air samples for chlorine content.
Drs. A. BONETTI and B. CARLI -- University of Florence,
Consiglio Nazionale delle Ricerche, Istituto di Ricerca sulle Onde Elettromagnetiche, Italy -- 80-297. Submilli meter-Infrared Balloon Experiment (completed).
Rotational spectra of key stratospheric molecules have been measured by a submillimeter Polarizing Interferometer that had been employed in the stratospheric flights. Resolution of the instrument is 0.0033 cm -1 . Spectra of H202 have been measured between 10 and 40 cm -1 , and the various lines identified. The spectra of the following molecules have been obtained between 10 and 72 cm -1 : CO, 0
3
, H
2
0, H
2
0
2
, N
2
0, NO, N02, HN0
3
, N0
3
, S0
2
, H
2
S,
HOC1, NOC1, and HCNO. The positions of the lines have been determined using a peak finder program, which allows a high precision of 2 x 10 4 cm -1 with respect to the calculated reference frequencies.
See Bonetti, et al., 76-137, and Trombetti, et al., 83-472.
-35-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
DR. F. BRUNER -- Urbino University,-Italy--- 81-365. Joint
Calibration Study of F-21 (completed).
The presence of CFC 21 in the atmosphere has been detected at two separate locations by two research groups independently, and results differing by an order of magnitude have been obtained.
The intercalibration study between the two groups (see Rasmussen, 81-356) showed--excellent agreement between the two different methods used for sampling and-measuring.
Dr. H. L. BUIJS -- Bomem, Inc. -- 75-90. Construction of a Fourier
Transform Spectrometer (completed).
A spectrometer with a projected resolution of 0.02 cm -1 was constructed for use in the simultaneous determination of CION0
HC1 and HF. See Buijs, 75-98 and 77-156.
2
and either HC1 or HF, or of
Dr. H. L. BUIJS -- Bomem, Inc. -- 77-168. Measurement of Halogen Compounds for Determination of Total Chlorine and Total Fluorine in the Stratosphere Using Long-Path
Interferometric Spectroscopy (completed).
A library study showed that there were very few published experimental data of sufficient resolution and quality for the interpretation of solar IR spectra.
Dr. H. L. BUIJS -- Bomem, Inc. -- 77-221.
Measurement of Infrared Spectra of Selected Stable Molecules
(completed).
Fourier transform infrared spectra of methyl chloride in the 3.3 pm region and of phosgene, carbonyl chlorofluoride, and carbonyl fluoride in the 1.3 lim to 5.6 Um region have been recorded at 0.01 cm-1 resolution both at room temperature and at stratospheric temperature (~240 K). The low-resolution spectrum of methyl chloroform from about 2.1 um to 5.6 Pm showed no useful features for detection of this species in the atmosphere.
Dr. J. A. COXON -- Dalhousie University -- 78-255, 80-315.
The A 2 π i
 X 2  i
Band System of C10: Absolute Absorption
Cross Sections at High Resolution for Bands of
Stratospheric Interest (completed).
-36-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
The ultraviolet absorbance of C10 produced at 315 K and 1.0-2.0 torr has been determined with a resolution of 0.0054 nm for all 35 C10 v'-O A 2
Π
3/2 -X 2 Π 3/2 sub-bands in the range 3≤ V'≤ 12. The experimental absorbance profiles for each sub-band have been reproduced closely by synthetic spectrum calculations with parameters optimized by nonlinear leastsquares techniques. The fitted band strengths lead to a well defined electronic transition moment variation for the A-X system of CIO. Absorption cross sections calculated at 222 K have been used as data in calculations of synthetic absorption spectra for a CIO column density of 10 15 cm -2 at two different spectral resolutions (0-02 and
0.15 nm).
Dr. D. D. DAVIS -- University of Maryland -- 74-10.
Laboratory Determination of the Sensitivity of
LaserInduced Fluorescence for the Detection of C10 under
Atmospheric Conditions (completed).
Ground-state stationary C10 concentrations of about 10 12 cm -3 were scanned at several electronic absorption wavelength regions with a tunable UV laser.
Laser-induced fluorescence proved to be unusable for measuring CIO.
Dr. D. D. DAVIS -- University of Maryland/Georgia
Institute of Technology -- 75-73. Laboratory
Measurement of Spectroscopic Absorption Cross Sections of
C10 (completed).
A frequency doubled tunable dye laser with a band width of 0.0015 nm was used to measure the absorption cross sections of C10 as a function of wave length for the A 2
∏
3/ 2 9-0 band. There was overall lack of resolution in the data, and an unassigned peak was observed at 283.06 nm. Simulated spectra indicated that a baseline resolved spectrum is not feasible, that the unassigned peak could be a 37 ClO absorption, and that the 35 C10 line width is somewhat wider than reported by Coxon and Ramsay. The real cross section attributable to
35C10 at 282-94 = (the largest peak in the spectrum) is calculated to be o R 19.5 = 1.04 x 10 -16 cm 2 .
Dr. D. D. DAVIS -- University of Maryland/Georgia
Institute of Technology -- 75-87. Development of
Instrument for Stratospheric OH Measurement by
LaserInduced Fluorescence (completed).
A miniaturized dye laser module for balloon flights has been built and tested.
-37-
, Ai.

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Dr. A. E. J. EGGLETON -- Atomic Energy Research
Establishment, Harwell, England -- 76-116. Total Chlorine
Measurements in the Troposphere and Stratosphere
(completed).
The feasibility of measuring total chlorine and fluorine in the atmosphere by neutron activation and photon activation, respectively, after collection of reactive species and particulate material on filters and collection of gaseous compounds on activated charcoal was studied. The proposed method proved unsuitable for the determination of total chlorine and fluorine contained in unreactive organic compounds due to a combination of insufficiently low halogen blank values in the best activated charcoal prepared and to inadequate adsorptive capacity for the more volatile organic compounds.
Dr. J. W. ELKINS -- National Bureau of Standards -- 83-473.
Measurement of the Temperature Dependence of the Infrared Band Strengths for CFC 11 and CFC 12.
The temperature dependence of the infrared band strengths for CFC 11 and CFC
12, needed to estimate their effects on surface temperature, will be measured.
Dr. K. M. EVENSON -- National Bureau of Standards, Boulder -- 84-533.
Line Broadening and Line Strength Studies Using a TuFIR Spectrometer.
The line broadening parameters of the 118 cm-1 line of OH be measured as a function of pressure using tunable far infrared spectroscopy.
Dr. C. J. HOWARD -- National oceanic and Atmospheric Administration,
Boulder -- 75-47. Laboratory Determination of the Feasibility of Laser
Magnetic Resonance for C10 Detection and Reaction Studies (completed).
It has been demonstrated that C10 can be detected by laser magnetic resonance with a sensitivity of about 10.10 molec cm -3 . Current maximum model predictions are about 108 molec cm -3 , and measurements have approached 109 molec cm -3 at 30 km.
-38

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Dr. C. J. HOWARD -- National oceanic and Atmospheric Administration,
Boulder -- 80-299. Infrared Spectroscopy of Atmospheric Species.
This measurement program is to provide accurately calibrated high-resolution infrared spectra of shorter lived atmospheric species for the identification and quantification of these constituents in the stratosphere. A Fourier transform infrared spectrometer has been delivered and is operational. The first species to be studied is peroxynitric acid.
Dr. H. D. KNAUTH -- University of Kiel, F.R.G. -77-171. Laboratory Study of the UV and IR Spectra of HOCI, HOON0
2
, and HC104 in the Temperature
Range of the Stratosphere (completed).
It was not possible to obtain partial pressures of H0
2
NO
2
greater than 0.1 torr in the N
2
0
5
/H
2
0
2
system in Pyrex vessels. The spectrum for gaseous HOC1 was derived from extinction measurements on the C1
2
/H
2
0 system at 333 K for different values of the equilibrium constant for the reaction
H
2
+ C1
2
0  2HOCI. The results are not in complete agreement with those of
Timmons (76-129), so additional work on the absorption centered around 300 nm is required.
Dr. H. D. KNAUTH -- University of Kiel, F.R.G. --
77-224. Laboratory Study for Determination of the
Equilibrium Constant of the reaction C1
2
0 + H
2
0  2HOCl and the UV Spectrum of HOC1 (completed).
The gas phase system C1
2
0 + H
2
0 = 2HOC1 has been investigated by UV from 200 to 500 nm at 333 K. Isobestic points were found at 214, 233, 335, and 380 nm.
The equilibrium constant 0.132 ± 0.008 and HOC1 cross sections were derived from absorbance measurements of the mixtures at equilibrium. The resulting
HOC1 spectrum shows absorption bands with peaks at 240 and 310 nm. Very clean
C1
2
0/H
2
0/ HOC1 mixtures proved to be remarkably stable. Thermal decomposition produced C1
2
with intermediate formation of C10
2 sections Of C1
2
0, C10
2
, and C1
2
. The absorption cross
were determined separately at 333 K.
Dr. W. J. LAFFERTY -- National Bureau of Standards --
84-501. Laboratory Studies to Support the Determination of HOC1 in the Stratosphere.
_39-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
The V
2
and V
3
bands of HOC1 will be recorded and the individual rotation-vibration transitions assigned. A line atlas will be produced listing the wave number, rotational quantum number assignment, and the line strength for each transition. Measurements and assignments have been completed for the u? band at under 0.004 cm-1 resolution.
Drs. F. J. LOVAS and R. D. SUENRAM -- National Bureau of
Standards -- 81-350. Millimeter Measurements and
Spectral Predictions of Stratospherically Important
Species (completed).
Detailed line positions and line strengths have been determined for HOC1 and
ClON0
2
. They will permit the detection of these species in the stratosphere from their microwave emission.
Dr. J. E. LOVELOCK -- Private -- 76-120. The Electron
Capture Detector as a Reference Standard for Analysis of Atmospheric Halocarbons (completed).
A theoretical model of the operation of the electron capture detector was developed. Application to the procedure used at the Adrigole station and on the RV Shackleton (1971-2) indicate that measurements at these bases are within 3% of theoretical predictions for CC1
4
and CFC 11. This evaluation was extended to CH
3
CCl
3
measurements..
Dr. J. E. LOVELOCK -- Private -- 78-226, 78-264, 80-293.
Development of Primary Fluorocarbon Standards (completed).
An exponential dilution technique, using a converted barn as the dilution chamber, has been developed to provide absolute calibration of standards for fluorocarbon concentration measurements.
Two standards from the ALE Program, each containing CFC 11 and CFC 12, have been repeatedly analyzed by exponential dilution and for CFC 11 by coulometry and the results compared with each other and the stated value for the ALE standards. The dilution-chamber and coulometry absolute calibrations agreed to within a few percent and were some 2% (11) and 4%
(12) below the stated values, giving high confidence in the absolute calibrations. Extension of the technique to methyl chloroform and carbon tetrachloride was less successful, with
-40-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements the form of the dilution relationship suggesting frequent partial absorption of the less volatile chlorocarbon on the glass ampoule from which it is released into the 50 m 3 chamber.
Dr. J. E. LOVELOCK -- Private -- 81-348. Consulting in Association with the Atmospheric Lifetime Experiment (ALE).
Data collected earlier have been assembled and analyzed to provide an absolute calibration by coulometry for the carbon tetrachloride (CC1
4
) concentration in some ALE calibration tanks.
Dr. K. MOE -- Private 78-235. Effect of Aerosol
Scattering on Ozone Measurements with the Dobson
Spectrophotometer (completed).
The NCAR UV double monochromator (UVDM) and associated computer programs have been shown to be capable of ozone measurements of hitherto unobtainable accuracy, while simultaneously measuring aerosol optical depth as a function of wavelength in the region of strong ozone absorption. An ozone value of 0.328 ± 0.006 cm was obtained at 10:00 h MST for June 8,
1978, compared with a corrected Dobson measurement of 0.340 cm at 12:05 h
MST.
The increasing number of UVDMs being deployed could provide accurate ozone data to resolve the discrepancy between predictions of ozone decrease from photochemical models and Dobson measurements, which show no decrease or increase.
Dr. D. G. MURCRAY -- University of Denver -- 75-92,
77-152, 78-265, 81-364, 82-413, 82-423. Laboratory
Measurement of High Resolution Infrared Spectra of Molecules of
Stratospheric Interest.
High resolution infrared spectra of compounds of interest in stratospheric chemistry have been measured. Statistical band-model analyses and integrated intensity measurements for the 10.8 pm band of CFC 12 and
11.8 pm band of CFC 11 have been published. A compendium of laboratory IR spectra (resolution 0.04-0-06 cm -1 ) has been prepared, and a list of the compounds studied as well as the detailed spectra are available to investigators upon request to CM.A, attention Fluorocarbon
-41-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Program Manager. An atlas of spectra for approximately thirty molecules is available from the University of Denver, and a handbook of spectra measured earlier is available from the CRC Press.
Dr. R. W. NICHOLLS -- York University, Canada -- 75-11 and 75-11-11. Experimental and Theoretical Studies on the UV Spectrum of C10 with Stratospheric Applications (completed).
Absolute absorption coefficients and cross sections have been measured for all bands and the photodissociation continuum of the v" =O progression for
ClO. The very complicated emission spectrum that has been excited over the wavelength range 2500-4500 A in discharges through C10
2
and C1
2
0 is currently undergoing measurement, identification, and analysis.
Computer-based synthetic spectra of various CIO bands have been calculated. Current work, which emphasizes the (2,0), (3,0), and (4,0) bands, should be of immediate diagnostic application to ground-based and balloon-based stratospheric spectroscopic observations.
Dr. R. W. NICHOLLS -- York University, Canada -- 75-30b.
Laboratory Studies of the Infrared Vibration-Rotation Spectrum of C10
(completed).
Work in this area was suspended to allow greater effort in the UV measurements (Nicholls, 75-11).
Dr. R. A. RASMUSSEN -- Private -- 76-142, 78-247.
Interlaboratory Comparison of Fluorocarbon
Measurements (completed).
A second round of identical samples of rural air has been circulated blind to participating laboratories for analysis for CFCs 11 and 12, CHC1
3
,
CH
3
CC1
3
, CC1
4
, and N
2
0- overall the results obtained showed a spread similar to that obtained in the 1976 NASA workshop. However, as in 1976, there was excellent agreement between Rasmussen and Lovelock, who use two different methods of calibration. A third round of samples was analyzed by 19 laboratories. Good agreement (±5%) was obtained by the 5 laboratories using common primary standards, but the other 14 laboratories showed much larger variations, with mean values considerably lower than those of the 5 laboratories.
-42-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Dr. R. A. RASMUSSEN -- Oregon Graduate Center -- 81-356.
Joint Calibration Study of F-21 (completed).
Two sets of pressurized tanks have been prepared from clean air and doped with differing amounts of CFC 21 up to 100 ppt. The tanks have been analyzed by Rasmussen's published mass spectrophotometric technique both before and after they were measured by Bruner (See 81-365). Agreement between the two laboratories is excellent and within one standard deviation on the measurements.
Dr. R. J. SAYKALLY -- University of California,
Berkeley -- 80-300. Near- and Far-Infrared
Spectroscopy (completed).
This project sought to develop far-infrared laser electric resonance as a technique for detection and measurement of transient species, with parallel-work in tunable F-center laser spectroscopy. The methods have potential applications in both laboratory kinetics and stratospheric measurements. The apparatus for both experiments was completed.
However, the laser electric resonance project was not pursued under this contract. The color center laser was used to develop a sensitive detection method for No and OH known as "tone burst modulated infrared laser absorption spectroscopy." The work will be extended to other molecules such as H0
2
, HOC1, and HONO under other funding.
Drs. P.G. SIMMONDS and J. E. LOVELOCK -- Private -
79-269. Determination of Tropospheric Halocarbons and Their Relative Importance (completed).
A routine, practical method for the direct determination of ambient CH
3
5-ml samples to ±5% has been developed based on a 63A electron capture
C1 in detector with oxygen-doped carrier gas. A special chromatographic column, which is a combination of OV101 silicone and Parasil E coated with SP1000 phase, specifically separates CH
3
C1 from all of the anticipated halocarbon interferences in ambient air. Daily measurements of ambient CH
3
C1 during
January, 1981, ranged from 553 ppt to 2470 ppt. The high values, associated with maritime air, suggest that the overall global budget for CH
2 been underestimated.
C1 might have
-43-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Concentrating 60-ml air samples with silica gel as an absorbent improves the precision of analysis for CH3C1 to ±1.7%. From retention volume data it has also been demonstrated that 0.5 g of silica gel would be sufficient for the quantitative adsorption of other important halocarbons such as CFC 22 and CFC 114 in a 100-ml air sample.
A portable gas chromatograph has been constructed for on-site analysis of river and sea water samples. Initial surveys indicate that the concentration of both CH
3
C1 and CH
3
1 in river water is approximately half that found in sea water, implying that river water is a hitherto unrecognized significant source of alkyl halides.
Chemical conversion methods were in general unsuccessful, and, of a large number of carrier gas dopants explored, only oxygen doping gave sufficient sensitivity for direct ambient analysis. Other potentially useful detectors, such as the photoionization and electrolytic conductivity detector, were also found to have inadequate sensitivity for determining trace levels of ambient halocarbons.
Dr. R. K. SKOGERBOE -- Colorado State University -
77-206. Development of a Measurement System for the
Determination of Total Chlorine in Air (completed).
The technique involves two flame reactions. The first, in a H2-rich flame, forms HC1, which is treated with indium to yield InCl. The InCl is then excited in an air-rich flame and detected photometrically. Blind analyses of calibration samples proved that the sensitivity of the technique was not sufficient to be of value for stratospheric measurements. However, it is hoped that the system can be put to use in tropospheric monitoring.
Dr. D. H. STEDMAN -- University of Michigan -- 74-7.
Atmospheric Determination of C10 Concentration: A
Feasibility Study (completed).
Laboratory studies have demonstrated the feasibility for detecting stratospheric C10 by chemical conversion to Cl (by reaction with NO) accompanied by vacuum ultraviolet resonance fluorescence. In-flight use of this technique is being supported by NASA.
_ 44-

2.
Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Dr. D. H. STEDMAN -- University of Michigan -- 76-132.
Absolute Calibration of Fluorocarbon Measurements
(completed) .
A feed-back flow system for the calibration of CFC samples has been built.
Dr. D. H. STEDMAN -- University of Michigan -- 77-151.
Generation and Exchange of Calibrated Samples of Fluorocarbons
(completed).
Work on this project was stopped because of feasibility problems.
Dr. R. B. TIMMONS -- Catholic University -- 76-129.
Photochemical and Chemical Kinetics Measurements of
Stratospheric Importance with Respect to the
Fluorocarbon Issue (completed).
HOC1 is a possible stratospheric sink the magnitude of which would depend on the absorption cross section. Earlier spectral measurements were inaccurate.
Pure HOCI cannot be prepared, for an equilibrium mixture Of C1
2 exists. The equilibrium constant for this reaction is K
P the UV absorption cross sections Of C1

0 and HOC1
0-8. This value and
2
0 have been used to determine the UV absorption cross sections of HOCI between 200-330 nm. The 230-240 nm peak was lower than previously measured, and no peak was found at 320 nm.
Dr. R. B. TIMMONS -- University of Texas, Arlington -
77-214, 78-258. Photochemical and Chemical Kinetics
Measurements of Stratospheric Importance with Respect to the Fluorocarbon Issue (completed).
The UV absorption cross sections of HOC1 between 200-330 nm over longer pathlengths have been determined under conditions such that interference by
C1
2
0 is minimal, i.e., low C1
2
0 concentration and excess H
2
0. An induction period for the increase in UV absorption at 320 nm was observed, suggesting that the 320 nm absorption may be due to more than one species.
The equilibrium constant for the C1
2
0 + H
2
0 reaction appears to be essentially temperature independent over the temperature range 25 to 57 C.
-45-

Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Work was performed using a quadrupole mass spectrometer in an attempt at direct determination of the concentration of HOC1 and any other interfering species. This would make the measurement of the UV absorption cross section more accurate. Results obtained with this instrument were not reproducible, and no reliable estimate for the HOC1 concentration could be made.
Drs. W. A. TRAUB and K. V. CHANCE --
Smithsonian Astrophysical Observatory at Harvard University -
80-318, 81-375, 82-445, 83-489, 85-544. Far-Infrared
Laboratory Spectroscopy of Stratospheric Species.
Laboratory spectra of HOC1 and,ClON0
2
-have been studied at a resolution of about 0.03 cm -1 in the region 70 to 250 cm -l in order to establish the line positions, strengths, and pressure broadening effects of air on the lines and bands. All lines appear too weak to be observed in the stratosphere.
Pressure broadening coefficients for HF and HC1 are being measured, and a computer program has been developed for simulating observed atmospheric spectra. This work is being done in support of an ongoing balloon measurement program.
Laboratory spectra of the V
6
and V
5
bands of ClN0
3
in the 20 micron region will be measured and analyzed for use in the balloon-borne measurement of
ClN0
3
.
Upper limits for hydrogen peroxide concentrations in the 22 to 38 km range have been determined from spectra obtained during the first Balloon
Intercomparison Campaign. The value at 31 km is a factor of 1.8 lower than a recent calculated value.
Dr. A. TROMBETTI, et al. -- University of Bologna, Italy, and other Italian institutions -- 83-472. Laboratory
Measurements of Far-Infrared Spectra of Molecules of
Stratospheric Interest.
This project continues activity on laboratory measurements of the spectra of source, temporary reservoir, and radical species in the 5 cm -1 to 180 cm -1 region. A new model of the flight IROE Fourier Transform
Interferometer of higher resolution has been designed and built. The resulting resolution is 0.0018 cm -1 in the range_5-80 cm -1 , as compared with
0.003 cm -1 for the previous model. Similar higher
-46-

Drs. M. S. ZAHNISER and C. E. KOLB -- Aerodyne Research,
Inc. -- 81-355, 83-469. Quantitative Infrared Line
Strengths for H0
2
.
The absolute infrared absorption coefficients and temperature dependent collisionally-broadened line shapes for vibrational rotational bands of H0
2 are being determined with a tunable diode laser. The line positions, line strengths, and overall band strength were determined for the V
3
band of H0
2
Work is in progress on the V
2
band of H0
2
.
D. Tropospheric and Stratospheric Measurements
Dr. J. G. ANDERSON -- Harvard University 82-428.
Detection of Stratospheric OH, H0
2
, and H
2
0 by
Copper Vapor Laser.
A newly developed atomic copper vapor laser system, a water vapor detector, and an ozone detector will be employed to obtain profiles of these important species below 30 km. Problems with the computer system, now resolved, have caused the launch date to be postponed to Spring, 1985.
Dr. J. G. ANDERSON -- Harvard University - 82-429.
Resonance Fluorescence Measurement of C10 and
Related Species Using a Reel-Down Technique. resolution is also expected in the wave number region above 80 cm -1 .
See Bonetti, et al., 80-297.
A platform capable of elevating and descending repeatedly by means of a
Kevlar tether when suspended under a helium filled balloon will be employed for multiscannings at critical altitude intervals in order to investigate in detail the concentration of C10 and related species in the stratosphere between 20 and 42 km. The payload has been flown successfully twice.
Table 3 (continued)
Laboratory Studies Related to Potential Atmospheric Measurements
Dr. J. E. BECKMAN -- Queen Mary College, London, England--
79-282. Airborne Millimeter-Wave Determination of
Cl0 (completed)
-47-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Measurements of the C10 mixing ratio were made with an airborne heterodyne receiver operating in the 230-270 GHz range during six day- and night-time flights over France in 1980. 0
3
profiles of moderate height resolution were also derived. The same instrument was used to detect ozone from a ground site at 242 and 481 GHz.
Drs. A. BONETTI and B. CARLI -- University of Florence and Consiglio Nazionale delle Ricerche, Istituto di
Ricerca Sulle Onde Elettromagnitiche, Italy -- 85-543.
High Resolution Submillimeter Balloon Spectroscopy.
The objective of this project is to optimize the IROE High Resolution FT
Spectrometer for further balloon measurements of the rotational far infrared and submillimeter) emission of selected stratospheric trace constituents. See also Traub and Chance, 84-537.
Drs. A. BONETTI and B. CARLI; Dr. J. E. HARRIES --
University of Florence, Consiglio Nazionale delle Ricerche,
Istituto di Ricerca sulle Onde Elettromagnetiche, Italy;
National Physical Laboratory, England -- 76-137.
Submillimeter-Infrared Balloon Experiment (completed).
Vertical distributions and diurnal variability of H
2
0, 0
3
, N0
2
, HN0
2
, HC1, CFCs
11 and 12, C10, ClONO
2
, and other molecules were determined using the 9 to 15 micron infrared region and submillimeter wavelengths from 200 to 1000 microns.
Data from the October, 1978, flight have been reduced for CFC 11 and 12, 0
16 0 18 0 16 0, HN0
3
H
2
O, HDO, H
2
17 0,H
2
18 0, HF, H 35 Cl, H 37 Cl, HCN, CO, 0
2
3
,
16 0 18 0, and OH.
See Bonetti, et al., 80-297.
Drs. A. BONETTI, B. CARLI, F. MENCARAGLIA, and F. FORNI --
University of Florence and Consiglio Nazionale delle Ricerce, Istituto di Ricerca sulle Onde
Elettromagnetiche, Italy -- 82-389, 82-437. Balloon
Intercomparison Campaign.
See Ogawa and Iwagami -- 82-391 and 82-438.
Dr. F. BRUNER -- Urbino University, Italy -- 78-256.
Determination of F-21 and Other Halocarbons in the
Troposphere (completed).
_48-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Two analytical methods for the quantitative determination of atmospheric CFC 21 at 1-50 ppt concentration have been set up based on GC separation followed, respectively, by EC and MS. In both methods the permeation tube technique has been adopted as the primary quantitative standard.
A series of samples has been collected from rural and industrial areas in Italy and over the Red Sea and the Indian Ocean. Concentrations of CFC 21 ranged from a few ppt to as great as 40-50 ppt.
Dr. H. L. BUIJS -- Bomem, Inc. -- 75-90, 75-98.
Measurement of HC1 and HF in the Stratosphere by Fourier
Transform Spectroscopy (completed).
Balloon flights to Alaska (May, 1976) and New Mexico (September, 1976, and
March, 1977) have provided profiles for HF and HC1 concentrations. The HC1 profile (volume mixing ratio), but not the HF profile, appears to show a maximum at 23-25 km, where the volume mixing ratios are 8 x 10 -10 (HCI) and 10 -10
(HF). The HC1 value is similar to values obtained by other investigators.
Upper limits on the concentrations Of C
2
H
6
(mole fraction), respectively.
and CH3C1 are 0.6x 10 -9 and ≤ 1 x 10 -9
See Buijs, 75-221.
Dr. H. L. BUIJS -- Bomem, Inc., Canada -- 77-15.
Operational Costing for Flights Planned in 1977
(completed).
HCl and HF profiles were recorded by infrared techniques from a balloon launched in New Mexico on October 27, 1978. The HC1 mixing ratio increased from about 2 x 10 -10 at 20 km to about 1 x 10 -9 at 35 km. Similar values for HF are about 3 x 10 -11 and 3 x 10 -10 , respectively. The shape of the curve of HF/HC1 vs. altitude is in reasonable agreement with that of Farmer and Raper (1977) over the altitude interval 17-27 km but does not agree with the profile calculated from a 2-D model (1981 chemistry), especially below 25 km.
A balloon flight on October 13 was designed to measure HC1, HF, and ClONO
2
. A failure in the on-board recording system and problems with the telemetry link prevented obtaining usable data from this flight.
-49-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Dr. E. B. BURNETT -- Florida Atlantic University -85-547. Feasibility
Study of C10 Column Measurement from UV Spectra.
The feasibility of using an instrument similar to the OH Pepsios for the measurement of C10 by ground-based absorption of sunlight in the near UV will be investigated.
Drs. H. U. DUETSCH and K. F. KUENZI -- Federal Institute of
Technology ETH and University of Bern, Switzerland
81-371. Comparison of Umkehr and Microwave Ozone
Profiles (completed).
A 30-channel microwave spectrometer at Bern and a Dobson instrument at Arosa were used to measure the same air mass simultaneously. The microwave technique yielded 20-30% higher ozone values than the Umkehr technique. Comparison of standard deviations indicates that the Umkehr technique is more precise for layer 6 (t5-8%), whereas the microwave technique is more precise for layer 9
(±8%). The microwave technique is less affected by aerosols.
Dr. D. H. EHHALT Nuclear Research Establishment Juelich, F.R.G. 76-145.
Electron Spin Resonance Detection of Stratospheric Radicals (completed).
Under a program supported by the German Government's Department of Research and
Technology a cryogenic sample was collected at 30.5 km at 1600-1700 hr
(conditions of relatively low radical concentration) during Murcray's March,
1977, balloon flight. The frozen sample was analyzed by ESR, showing the following concentrations. N0 detected.
2
: ~3.5 x 10 8 ; H0
2
:~ 8-5 x 106 molec cm -3 ; C10: not
Dr. P. A. EKSTROM -- Battelle Memorial Institute, Pacific
Northwest Laboratories -- 75-27. Ground-Based Millimeter
Wavelength Observations of Stratospheric C10 (completed).
About 500,000 data points were obtained in the microwave spectra near 93 GHz with the Kitt Peak radiotelescope. Due to excessive noise no Cl0 signal could be detected.
Dr. A. GIRARD -- Office National d'Etudes et de
Recherches Aerospatiales, France -- 75-88.
Measurement of HC1, HF, C10, etc., in the Stratosphere by
High Resolution Infrared Spectroscopy (completed).
-50-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Vertical profiles of HC1, N0
2
, H
2
0, and CH
4
between 26 and 35 km have been deduced from two balloon-borne grating spectrometer experiments. There is a hint of a decrease in HC1 mixing ratio at the upper limit of the October, 1977, experiment. Laboratory infrared spectra have been obtained for ClN0
3
, N0
2
, HN0
3 and HCHO. The method of infrared limb sun pointing was found to be inadequate
, for the detection of C10 in the atmosphere.
Drs. A. GOLDMAN and A. BARBE -- University of Denver;
University of Reims, France-- 80-322, 83-457. Collab- orative Studies on Atmospheric Spectroscopy.
Groups from the Universities of Denver and Reims are collaborating to develop consistent inversion algorithms to obtain atmospheric concentration data for several trace species (e.g., HC1, HF, 0
3
) from infrared spectra measured from the ground or balloon platforms.. Atmospheric infrared spectra will also be used to gather information on weak lines of molecules such as 0 cannot easily be measured in laboratory systems.
3
and HN0
3
that
The two groups now get excellent agreement for the v? band of 03. Work is in progress on the V l
, V
3
region of 0
3
and on isotopic 0
2
.
Drs. D. W. T. GRIFFITH and P. J. CRUTZEN -- Max Planck
Institut fuer Chemie, Mainz, FRG -- 84-526.
Stratospheric Trace Gas Measurements Using Matrix Isolation-
FTIR Analysis.
A promising technique for the detection of nitrogen oxides and other stable and unstable species in the lower stratosphere is being tested. Air is sampled cryogenically at 77K, the sample taking the form of a C0
2
matrix with trace gases embedded in it, and analysis is done in the laboratory by FTIR absorption spectroscopy of this Some samples are frozen directly into the cyrostat
UT-which the absorption spectrum is to be measured later in the laboratory. In a second technique the sample is co11ected by pumping air through a liquid nitrogen cooled glass sampling coil. In the laboratory the sample is briefly evaporated and refrozen into the measurement cryostat.
_51-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
The preliminary results of test flights with a Lear jet over northern Europe identified some shortcomings to both collection techniques. Surprisingly, the direct frozen matrix was not firm enough to allow a sensitive analysis by FTIR.
Nevertheless, the matrix isolation technique combined with FTIR spectroscopy seems to be a powerful tool for the detection of trace species in the lower stratosphere due to its high sensitivity and selectivity.
Dr. W. S. HEAPS -- National Aeronautics and Space
Administration, Goddard -- 84-508. Balloon Lidar
Measurements of OH and 0
3
.
A balloon-borne Lidar system has been developed for stratospheric measurements of OH and 01. The FPP funding will permit an additional flight to be made in
1985.
Dr. P. JOUVE -- University of Reims, France -- 79-290.
Measurement of the Vertical Distribution of HCI, 0
3
, and
HCHO and the Ratio HF/HCI (completed).
Ground-based measurements of HC1, HF, NO, COS, 0
3
, and H
2
CO have been made using high resolution infrared spectroscopy. These measurements were made during 1981 from an observatory in Haute Provence, France, by a team from Jouve's group at the CNRS Laboratory located in Reims. The vertical profiles of HC1, 0
3
, H
2
CO, and the ratio HC1/HF have been obtained.
The last series of measurements has confirmed the possibility of obtaining high quality Umkehr measurement for ozone in the upper stratosphere.
Drs. W. D. KOMHYR, R. D. GRASS, R. D. EVANS, and
A.
N. CHOPRA -- National Oceanic and Atmospheric
Administration, Boulder, and University of Colorado -
81-363. Umkehr Observations with Automatic Dobson
Ozone Spectrophotometers (completed).
Modernization of six Dobson spectrophotometers is underway in order to permit automated Umkehr observations at selected locations worldwide. The automated instruments are expected to provide more frequent and more accurate Umkehr altitude profiles of ozone. Ozone trends at altitudes near 40 km are potentially a more sensitive warning of depletion by chlorofluorocarbons than total ozone trends. The prototype automated unit is installed at Boulder
(Colorado). Under this
-52-

Table 3 (continued)
Tropospheric and Stratospheric Measurements project, instruments have been automated and installed in Haute Provence
(France),,Poker Flats (Alaska), Mauna Loa (Hawaii), and Perth (Australia). An instrument will be installed at Huancayo (Peru~ during 1985, and one at an additional Southern Hemisphere location. This project is cofunded by EPA, NOAA, and WMO.
Dr. J. E. LOVELOCK -- University of Reading, England,
Private -- 73-1, 74-3, 75-67, 77-144. Fluorocarbons in the Environment (completed).
The electron capture gas chromatograph (ECGC) has been developed and applied to the measurement of several halocarbons in the lower stratosphere and troposphere, particularly over Europe and the Atlantic Ocean. In 1976 levels of
CFC 11 were about 130 ppt (U. K.) and 80 ppt (Southern Hemisphere). CH3C1, with the ocean and smouldering vegetation as identified sources, was at about 10-9 v/v in the Northern Hemisphere but was found to be higher over the southern
African continent (2.2 x 10 -9 v/v in Kenya) (cf. Rasmussen, 77-181, p. 54). CC14 and CH
3
CC1
3
were also unexpectedly high. Portable monitoring equipment has been provided and put to use in South Africa and Australia. The levels of CH
3
CC1
3 found in the Southern Hemisphere (50 ppt) appeared higher than expected from release and tropospheric lifetime estimates. Northern Hemisphere values were about 100 ppt.
Measurements of CFC 11 in the atmosphere and ocean were made during the April,
1977, voyage of RRS Challenger in the northeast Atlantic Ocean. Average air concentrations of 155 ppt were observed for CFC 11, and it was present at saturation quantities down to depths of 500 m.
See Rasmussen 76-142.
Dr. G. MEGIE -- Service d'Aeronomie, Centre National de la Recherche Scientifique, France -- 84-510. Ozone
Monitoring in the 35-45 km Altitude Range by an Exciplex
Laser-UV Lidar.
The laser will be received and tested in June. Ground-based measurements will be done in July at "Observatoire de Haute Provence."
-53-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Dr. D. G. MURCRAY -- University of Denver -- 75-13, 76-101,
76-135, 77-166. The Measurement of the
Stratospheric Distribution of Fluorocarbons and
Other Constituents of Interest in the Possible
Effect of Chlorine Pollutants on the Ozone Layer
(completed).
Measurement of stratospheric distribution by balloon-borne, high-resolution, infrared absorption measurement at large solar zenith angles has been achieved using a specially constructed grating spectrometer. The distributions obtained for CFCs 11 and 12 and CC1
4
showed a concentration increase of about 2.5, with a rather wide range of uncertainty, from 1968 to 1975 for CFCs 11 and 12.
Subsequent flights also yielded HC1 and HN0
3
profiles. A preliminary value of 2 ppbv for the concentration of ClON0
2 at 26 kin has been calculated. The upper limit for H
2
0
2
ks 1 ppbv at 20 km.
An October, 1978, balloon flight with an interferometer system instead of a grating system was successful and recorded through sunset with the last record obtained at solar zenith angle > 95 0 . A strong absorption at 1283 cm -1 is due to
CF
4
with an estimated mixing ratio of 75 pptv at 25 km. The ClON0
2
mixing ratio is 0.8 ppbv from 24 km to 32 km, then falling to 0.4 ppbv at 33.5 km. Several features coincide with some of the HOC1 lines, but the agreement appears fortuitous, and no features can be assigned with certainty to HOC1. The upper limit for H
2
0
2
is 0.5 ppbv at 20 km and for C0F
2
is 0.4 ppbv at 25 km.
The latest flight of the series was performed on October 20, 1981. The float altitude at sunset was 32.3 km. Two interferometer systems and a pressure modulated radiometer were on board. The principal objective of the flight was to obtain measurements of ClONO
2
, which has been tentatively identified. Mixing ratio profiles of ClON0
2
have been determined for flights made October 27,
1978, and March 23, 1981.
Dr. D. G. MURCRAY -- University of Denver -- 77-211.
Acquisition of an on-Board Digital Recording System
(completed).
The balloon-borne interferometer system has been improved by incorporating into it on-board recording capability.
_54-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Advantages are two-fold: a back-up is provided in case the telemetry system malfunctions, and it becomes possible to operate under atmospheric wind conditions that might carry the balloon out of telemetry range. The system was used successfully for balloon flights on October 28, 1978, and October 20,
1981.
Dr. D. G. MURCRAY -- University of Denver -- 78-228.
Detection of Selected Molecules by Ground-Based Solar
Spectroscopy (completed).
Solar spectra were examined with a resolution of 0.01 cm -1 . An atlas of the
775-950 cm -1 and 1050-1300 cm -1 regions has been prepared.
A workshop on solar spectroscopy was held at the National Bureau of Standards,
March 26, 1980.
Dr. D. G. MURCRAY -- University of Denver -- 81-380, 84
497. Ground-Based Observations of Stratospheric Species.
Ground-based infrared techniques will be used to attempt measurements of temporary reservoir species (ClONO
2
, N
2
0
5
, H0
2
NO
2
) in the stratosphere.
Laboratory infrared spectral studies will be made in support of these studies.
Laboratory data have been obtained for ClON0
2
and N
2
0
5
at a resolution of 0.003 cm with ClONO
-1 . Ground-based spectra snow a feature at 780.21 cm -1 that may be associated
2
. This has been tentatively identified in balloon-based spectra.
Drs. D. G. MURCRAY and H. K. ROSCOE--University of
Denver; Oxford University, England---77-219. Stratospheric
HC1 Measurements Conducted as a Piggy-Back to
Murcray's Flight (completed).
Because the vibration problem with the solar-absorption pressure modulator radiometer used for the HC1 measurements could not be reasonably solved, this project was cancelled.
Drs. D. G. MURCRAY and H. K. ROSCOE --University of
Denver; Oxford University, England--80-328. An
Intercomparison of Measurements of Stratospheric HC1
(completed).
-55-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
The simultaneous measurement of stratospheric CION0
2
(rather than HC1) on a balloon flight with a high resolution IR interferometer (Murcray) and with a pressure modulator radiometer (Roscoe) was planned. Difficulties with encoding prevented obtaining useful results with the latter.
Drs. T. OGAWA and N. IWAGAMI -- University of Tokyo, Japan --
82-391, 82-438; Drs. G. M. STOKES, D. W. JOHNSON, and
G. J. SCHUSTER -- Battelle Memorial Institute, Pacific
Northwest Laboratories -- 82-397; and Dr. P. T. WOODS -
National Physical Laboratory, England -- 82-403, 82-432.
Balloon Intercomparison Program (BIC),* Phases One and Two.
These three projects form part of an extensive balloon measurement campaign, cofunded with NASA, the Council of European Communities (CEC), and others primarily to take measurements of HC1 and NOX at Palestine, Texas, in the fall of 1982 and the spring of 1983.
The campaign comprised the simultaneous launch of several balloons, each carrying a number of instruments. Measurements were taken simultaneously, in the same air mass, over a period of some hours. Evaluation of the data from these numerous devices will permit a better distinction between atmospheric variability and instrument characteristics.
Projects 82-403 and 82-432 contain subcontracts with Zander, University of
Liege (82-395 and 82-435); Bonetti, et al., University of Florence (82-389 and
82-437); Pommereau, CNRS (82-394 and 82-436); Taylor, University of Oxford
(82-393 and 82-434); as well as with Woods, et al., NPL (82-394 and 82-433). In all, some 20 investigators flew instruments enabling extensive intercomparisons of different techniques for measuring HC1 and NOX" as well as providing extensive data on other species.
In addition simultaneous measurements were made from the ground and from aircraft. Project 82-397, a ground-based experiment providing for measurement of solar absorption spectra from Kitt Peak during the period of the stratospheric measurements, yielded excellent HCI and HF absorption spectra during the first BIC flight and HN03 spectra for the subsequent day.
-56-

1.
Table 3 (continued)
Tropospheric and Stratospheric Measurements
The first phase of the BIC campaign, completed in September, 1982, was only partially successful. It was possible to launch four large balloons into the same air mass within a spread of three hours. However, one balloon failed, not all instruments were flown, and some instruments had problems.
Data from this first phase of the campaign have been analyzed by the investigators under the coordination of Seals of NASA Langley, whose group reduced some of the raw data.
The CMA investigators in this Program have reported the following results: sunset profiles for HC1 and CH4 and a daytime profile for HF (82-403), a profile for HN0
3
(82-394), qualitative identification of C10 (82-389), total column N0
2
from the ground and an N0
2
profile in the stratosphere during ascent
(82-394), and a profile for NO, together with other data on N0
2
, N
2
0
5
, and HN0 which are apparently affected by aerosol from the El Chichon eruption
3
,
(82;-393). Efforts will be made to evaluate any effect of aerosol from El
Chichon on all the data obtained.
The Spring, 1983, campaign was rescheduled for later in 1983 following two balloon failures during the May, 1983, launch. Additional experiments were included in the campaign to characterise the aerosol layer. These included aircraftborne instruments for remote sensing, climate observations, in situ sampling, and characterization of composition and size distribution of the aerosols, together with a small balloon-borne instrument on a fifth gondola for aerosol profiling.
In June, 1983, flights were accomplished without mishap by the University of
Liege and the JPL-2 gondolas. Unfortunately, the JPL-1 gondola and instruments were totally destroyed following free fall from 110,000 ft. The NPL gondola landed safely but was subsequently damaged when dragged during a storm. Several instruments were damaged and the Oxford PMR destroyed.
As analysis of the results has progressed, it has become evident that the BIC-I data set is somewhat limited for intercomparison purposes. This is not the case for BIC-II, and a remarkable quantity and quality of results have been achieved. The only significant failure was the JPL interferometer.
-57-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Several productive data analysis meetings have been held. A set of papers are being drafted for publication.
Dr. J. P. POMMEREAU -- Service d'Aeronomie,
Centre National de la Recherche Scientifique,
France -- 82-392, 82-436. Balloon Intercomparison
Campaign.
See Ogawa and Iwagami -- 82-391 and 82-438.
Dr. J. P. POMMEREAU -- Service dAeronomie, Centre
National de la Recherche Scientifique, France -
85-550. Participation in MAP GLOBUS NO x
Campaign.
Supplemental funding will be provided to enable several investigations to participate.
Dr. R. A. RASMUSSEN -- Washington State University
75-2, 75-59. Fluorocarbon Research (completed).
An attempt was made to obtain halocarbon concentration measurements as far into the stratosphere as could be reached by an available commercial aircraft. A small portable gas chromatograph was used for on-board measurements, and consisted samples were collected for subsequent detailed halocarbon analysis on the ground. One phase of the study consisted of samples collected over a wide area of the Pacific Northwest, a second of samples collected frequently to the maximum attainable altitude over Alaska. The halocarbon concentrations are either constant or decrease very slowly with altitude in the tropopause, decrease rapidly in the tropopause from the tropospheric concentration to an average value identifiable with the stratosphere, and do not show a clear pattern of concentration gradients above the tropopause.
A trans-Pacific flight from 8O O N to 60 0 S has been completed, and the air samples collected have been analyzed for halocarbons. Most of the samples were collected at 39,000 to 43,000 ft. CFC 12 concentrations are about 10% higher in the north than in the south at ground level, and the difference is apparently greater for CFC 11.
Dr. R. A. RASMUSSEN -- Private -- 77-181. Measurement of the Concentration of Methyl Chloride in Air in
Kenya (completed).
-58-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Air samples were obtained at ground level and by aircraft in Kenya and over the
Indian Ocean. Analyses showed CH3CI at 600-700 ppt over Kenya, rising to
900-2000 ppm in areas where slash burning was being conducted (cf. Lovelock,
77-144). Boundary layer analyses over the Indian Ocean were 750-880 ppm. N
2
0 levels were 324-378 ppb. Other analyses showed CFC 12, 235-246 ppt; CFC 11,
137-143 ppt; CH
3
CC1
3
, 74-96 ppt; and CC1
4
120-135 ppt. Comparison with previous data showed interhemispheric differences for the above five species.
Dr. R. A. RASMUSSEN -- Oregon 'Graduate Center -
78-260. Identification of FC-21 in the Atmosphere
(completed).
Measurements of CFC 21 in Tasmania, at the South Pole, and in "clean" air from
Cape Meares, OR, show concentrations of 0.05-0.6 ppt, compared with concentrations of 2 ppt at Harwell, U. K. 'GCMS identification confirms CFC 21, distinguishing CFC 21 from CH31- CFC 21 samples do not increase in CFC 21 content on storage, nor is CFC 21 produced from fluoroplastics examined, nor is
CFC 21 observable in CFC 11 or CFC 12 standards. CFC 21 is highly variable, and more measurements are needed.
Dr. R. A. RASMUSSEN -- Private --80-308. F-22
Measurements in the Atmosphere (completed).
The concentration of CFC 22 has been measured in 99 air samples collected between April, 1978, and January, 1981, with supplemental samples from 1977.
The average rate of increase in CFC 22 concentration over the last 3 years was found to be approximately 12%/yr. The atmosphere contains about 200 Mkg more than expected from the McCarthy, et. al., emission estimates. This discrepancy is small compared with the uncertainties in the absolute calibration, the accuracy of release estimates, and the limited global measurement coverage.
Dr. B. A. RIDLEY -- York University, Canada -- 76-102A,
76-102B. Measurement of Fluorocarbons and Related
Chlorocarbons in the Stratosphere by Collection and
Analysis (completed).
-59-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Series of evacuated stainless-steel spheres were used to obtain samples of stratospheric air at various altitudes up to 39 km from three balloon flights.
Some problems were encountered in the absolute calibration of the electron capture gas chromatograph, but the results are consistent with a stratospheric photolysis sink for CFCs 11 and 12 and N
2
0
Drs. P. M. SOLOMON and R. L. deZAFRA -- State University of New York, Stony Brook -- 76-130, 77-225, 79-278, 80-
316, 81-362, 82-410, 83-467, 84-521. Millimeter Wave
Observations of Chlorofluoromethane Byproducts in the
Stratosphere.
This study is directed toward the development of a groundbased method for continuous determination of C10. One of the millimeter wave observing systems is based on a 3-nm maser, a unique instrument that is the most sensitive detector in the world in the 83-94 GHz range.
A 256-channel radio frequency spectrometer has been built and tested for the analysis and identification of the weak pressure-broadened 93 GHz signal from stratospheric C10. An upper limit of 1.5 ppb C10 was measured with the 130 GHz receiver. In a joint effort with Bell Laboratories C10 has been detected at 204
GHz at the FCRAO radio astronomy observatory near Amherst, Mass.
Measurements of C10 have been made at 278 GHz during January March, 1981, at
FCRAO observatory and from Mt. Hopkins, Arizona, during April-May, 1981. A cooled mixer was used with this equipment, which made this equipment the most sensitive produced so far at this frequency. For the first time C10 has been detected at night. C10 data from Mt. Hopkins are in good agreement with predictions using 2-D models in contrast to Anderson's in situ C10 measurements, which are higher than model predictions above 35 km.
C10 measurements at 204 GHz were made during the spring of 1982 at the
University of Massachusetts observatory with a receiver that contained a cooled mixer. Results are consistent with the previous 204 and 278 GHz measurements.
Since September, 1982, five ground-based measurement campaigns have been made at Mauna Kea, Hawaii. The high altitude of
_60

Table 3 (continued)
Tropospheric and Stratospheric Measurements this site (approximately 4.3 km) minimizes interference from tropospheric water vapor. Diurnal measurements were obtained for Cl0 with a time resolution of two hours. Both H0
2
and HCN have also been detected at approximately 266 GHZ.
Drs. G. M. STOKES and D. W. JOHNSON -- Battelle
Memorial Institute, Pacific.Northwest Laboratories -
82-417. Review of Kitt,Peak Data Archives for Methane and Other Species.
Spectral data obtained at Kitt Peak National Observatory from 1978 through 1983 are being analyzed by Stokes and by Zander (see Zander, 82-439). Data have been used to derive a trend for atmospheric methane during this period and to look for selected trace gas species.
For trace species most effort has been directed toward C10 (around 820 cm -1 ) and
ClONO
2
. With the current signal to noise ratio, only an upper limit, which falls within the range of the in situ measurements, can be deduced for C10. The ClON0
2 signal is merged with lines of C0
2
and 0
3
.
See Zander 82-439.
Drs. G. M. STOKES, D. W. JOHNSON, and E. W. PEARSON -
Battelle Memorial Institute, Pacific Northwest
Laboratories -- 84-493. Analysis of Data on Stratospheric
Nitrogen Species.
The atmospheric burden of NO and NO
2
, will be studied by measurements using high resolution Fourier transform spectroscopy at the Kitt Peak National Observatory.
Major emphasis will be placed on the diurnal variation.
Drs. G. M. STOKES, D.-W. JOHNSON, and G. J. SCHUSTER
--Battelle Memorial Institute, Pacific Northwest
Laboratories -- 82-397. Balloon Intercomparison Campaign
(completed).
See Ogawa and Iwagami -- 82-391 and 82-438.
Drs. F. W. TAYLOR and H. K. ROSCOE -- Oxford University,
England -- 82-393, 82-434. Balloon Intercomparison
Campaign.
See Ogawa and Iwagami -- 82-391 and 82-438.
_61-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Drs. F. W. TAYLOR and H. K. ROSCOE -- Oxford University,
England -- 83-484, 84-532. Balloon Measurements, with
Pressure Modulators and Selective Absorbers.
The Pressure Modulator Radiometer used to measure stratospheric NO and N0
2
was damaged in a 1983 balloon flight. It is being rebuilt to an improved design.
Dr. 0. C. TAYLOR -- University of California at Riverside
--73-3, 74-2. Monitoring and Atmospheric Reactions of
Fluorocarbons (completed).
An electron capture gas chromatograph was used to measure the concentrations of
CFCs 11 and 12 in the troposphere over southern California and in the lower stratosphere over New Mexico and Colorado. The tropospheric concentrations were found to vary from day to day as climatic conditions affected dispersion and dilution. Concentration decreased with increasing altitude in the lower stratosphere.
Drs. W. A. TRAUB and K. V. CHANCE -- Smithsonian
Astrophysical Observatory at Harvard University --
84-537. Construction of a Duplicate Single Axis
Platform.
A single axis platform will be built for accurate control of the viewed elevation angle of far infrared spectrometers. The platform is for use by the
U. of Florence/IROE team. The improved pointing accuracy will result in greater altitude resolution of retrieved stratospheric constituent profiles. See also
Bonetti and Carli, 85-543.
Dr. P. T. WOODS -- National Physical Laboratory, England
-- 82-403, 82-432. Balloon Intercomparison Program.
See Ogawa and Iwagami -- 82-391 and 82-438.
Drs. P. T. WOODS, S. POLLITT, M. J. BANGHA14, R. H.
BRADSELL, D. G. MOSS, and N. R. SWANN -- National
Physical Laboratory, England -- 82-394, 82-433. Balloon
Intercomparison Campaign.
See Ogawa and Iwagami -- 82-391 and 82-438.
-62-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
Dr. R. A. YOUNG -- Xonics, Inc..-- 75-50, 75-86. Development of an
Instrument to Measure 0, CIO, 0
3
, and Total C1 in the Stratosphere
(completed).
A preliminary evaluation of-resonance fluorescence for the stratospheric measurement of CIO and total chlorine was made during the September, 1975,
STRATCOM balloon flight. This work and subsequent laboratory work indicated that alternative methods for these measurements hold greater near-term promise.
Dr. R. ZANDER -- University of Liege, Belgium -- 76-141, 78-232.
Ground-based Infrared Measurements (completed).
The 7.5-meter focal length double-pass infrared spectrometer at the Jungfraujoch
International Scientific Station (altitude 3580 m) was used to monitor atmospheric column densities of HF and HC1. Resolution of the instrument is about
0.02 cm -1 . The HF concentration has increased about 10% per year over the
Jungfraujoch between the years 1976 and 1983. Similar data from Kitt Peak indicate a 5% per year increase of HF between the years 1969 and 1979. The relative concentration of HF at both stations supports a meridional increase versus latitude. There is no sign of an increase in HCI during the same period although there is a meridional increase versus latitude. Frequently a high variability in the HCI column density, which may be due largely to the troposheric component of the HCI column, was observed.
CION0
2
is qualitatively observable from the ground at 780.21 cm -1 in Kitt Peak solar spectra and with the new FTIR instrument at Junjfraujoch- CFC 11, CFC 12, and CFC 22 are also observable in the 8-12 micron region. Better definition of line strength and temperature dependence should also permit measurement of C10 with a ground-based spectrometer. The CH
4
trend above the Jungfraujoch station was determined_ in the spectral data since 1952.
See Ogawa and Iwagami -- 82-391 and 82-438.
Dr. R. ZANDER -- University of Liege, Belgium--82-395,
82-435. Balloon Intercomparison Campaign.
Dr. R. ZANDER -- University of Liege, Belgium--82-439,
84-517. Interpretation of Kitt Peak Spectra.
-63-

Table 3 (continued)
Tropospheric and Stratospheric Measurements
The Kitt Peak National Observatory data archives have been searched for atmospheric species of interest. These include HNO
3
, N
2
0, NO, NO
2
, HCHOOH,
HF,HC1,and CH
4
. Revised laboratory data indicate that it should be possible to deduce an upper limit for HOC1.
Observations at the Jungfraujoch have been carried out to investigate the variability of atmospheric trace gases and to refine the trends for CH
4
,
HC1, and HF.
See Stokes 82-417.
E. Modeling
Dr. G. BRASSEUR -- Institut d'Aeronomie Spatiale,
Belgium -- 80-320, 82-396, 83-468, 84-534. Modeling of the CFC Effect on the Ozone Layer.
A Fourier Transform Spectrometer providing a spectral resolution of 0.005 cm -1 has been operating at the Jungfraujoch station since the end of 1984.
This instrument, although primarily designed for the wave length range
1.5-5.5 Um, has been converted to the more interesting region of B-13 um.
After optimal performance is achieved, measurements will be taken routinely with higher resolution than can be obtained with the grating instrument.
A one dimensional model that can be used to study the diurnal variations of short lived trace species and to evaluate the variation of atmospheric temperature profiles due to changes in the concentration of the radiative active gases is available. Time-dependent, coupled-perturbation calculations have been performed with several emission scenarios for CFCs,
CH
4
, N
2
0, C0
2
, and aircraft N0 x
. The calculated changes in total column ozone are less than ± 1% for scenarios simulating the past emission of these trace gases and extrapolating them into the next century. Measured stratospheric CH
3
CN profiles were analyzed for use as a tracer for the active chlorine concentration in the upper stratosphere. The unexpectedly slow rate constant for the reaction of C1 with CH
3
CN prevented such a use.
The model will continue to be used for the evaluation of speculative chemistry, and an improved 2-D model will be developed.
-64-

Table 3 (continued)
Modeling
Dr. G. BRASSEUR -- Institut d'Aerononie Spatiale,
Belgium -- 84-505. Incorporation of Chemistry into the
Free University of Berlin 3-D Model
Cooperation between the two groups is being increased by support of a student from the Free University of Berlin at the Institut d'Aeronomie Spatiale.
Drs. D. M. CUNNOLD, F. N. ALYEA, and R. G. PRINN -
CAP Incorporated -- 75-24, 76-122, 77-199, 78-252,
79-281, 80-323, 81-361, 82-422. Meteorological and
Multi-Dimensional Modeling Considerations Relating to
Atmospheric Effects of Halocarbons (completed).
Studies to assess the accuracy and shortcomings of the I-D model used to estimate ozone depletion indicated that a tropospheric lifetime for CFCs 11 and
12 as short as 10 years was not inconsistent with atmospheric measurements.
Thus, ozone depletion estimates might be considerably less than present estimates. The great variability of stratospheric measurements indicates that simultaneous measurements for many important stratospheric species are needed and that seasonal dependence of species must be considered.
The neglect of dynamical feedback processes in the radiative models used to calculate warming (greenhouse effect) limits the value of calculated effects.
Preliminary calculations have been made including feedback effects due to inclusion of the hydrological cycle and circulatory effects. Preliminary results indicate that inclusion of- the hydrological cycle would strongly counteract the greenhouse effect, whereas circulatory changes would slightly increase it.
Because it has been shown that meteorological conditions can cause variations in both tropospheric and lower stratospheric fluorocarbon measurements in
Alaska, temporal and latitudinal variability of fluorocarbon concentration has been estimated, and the results related to the sensitivity of trend detection in the Atmospheric Lifetime Experiment (cf. 82-422) and to previous interhemispheric observations.
A preliminary estimate was made for the lifetime of a tropospheric sink due to photodecomposition of CFCs on sand. The sink would imply a lifetime of 30 years if 40% of the CFCs were destroyed over the Sahara Desert.
_65-

a
Table 3 (continued)
Modeling
A methodology was developed for determining the lifetime of tropospheric sinks of CFCs by daily monitoring. This methodology is being implemented under
82-421, 81-376, 81-377, and 83-476.
The surface temperature increase resulting from atmospheric CFC mixing ratios increasing to 2 ppbv has been reestimated at 0.2 ± 0.5
0 C (95% confidence limits). The significance of its impact is thus extremely uncertain and is only one of a number of factors that could induce climatic change.
M. KINOSHITA -- Mitsubishi Research Institute, Japan -
83-461. One Dimensional Radiative-Convective Model of the Atmosphere..
This project entails the upgrading and optimization of MRI's 1-D photochemical-eddy diffusion model through inclusion of tropospheric chemistry, development of diurnal capability, inclusion of coupled perturbations, and development of a radiative-convective model.
Development of the reactive-convective model has been completed. Improvements have been made to the 1-D photochemical eddy diffusion model. Efforts are being focused on the coupling of these two models.
Dr. N. D. SZE Environmental Research and
Technology, Inc. 75-32, 76-115. Model Analysis of
The Fluorocarbon Problem (completed).
A one-dimensional model has been used to evaluate the role of stratospheric water in the NO x
and Cl x
cycles, the relationship of eddy diffusion coefficient and CFC lifetime, the use of CFC measurements to calculate lifetime, and the effect of chlorine nitrate. The importance of OH concentration on calculated ozone depletion was shown, and key reactions were identified. Analyses showed
10-20 year tropospheric lifetimes were not inconsistent with measurements and helped to define quantitatively the uncertainties associated with ozone depletion calculations.
Inclusion of multiple scattering in the model had a negligible effect on the ozone depletion estimates. The modeled ozone profile above 40 km is a factor of
2-3 lower than recent measurements. Calculated CIO profiles are a factor of 2-4 too low at 28-35 km when compared with Anderson's CIO data.
-66-

Table 3 (continued)
Modeling
A diurnal model has been developed that permits calculation of stratospheric concentration profiles of any HO x
, ClO x
, or 0 x
species.
Dr. N. D. SZE -- Atmospheric and Environmental Research,
Inc. -- 77-173, 78-234, 79-273, 80-311, 81-366, 82-405,
83-465, 85-523. Theoretical Models of Stratospheric
Chemistry,Perturbations, and Trace Gas Measurements
(continuation of 76-115).
Iterative procedures, which lower the computer time by a factor of 3 for the diurnal model, have been developed.
The modeled HF/HCl ratios using 1978 rate data are at least a factor of 2 higher than the measured values. A possible explanation is that OH is less than model predictions, thus indicating a greater reservoir of inactive chlorine. If the rate of formation of OC100 is sufficiently rapid, it can constitute a
"holding tank" for active chlorine.
Theoretical calculations indicate that the possibility of a 20-year tropospheric sink due to adsorption of CFCs 11 and 12 on desert sand with subsequent photodecomposition by sunlight cannot be ruled out.
A 2-D model with full diurnal capability has been developed with joint CMA FPP and Air Force funding. This represents a substantial upgrading of the 2-D model.
Analysis of the vertical gradient for CFCs 11 and 12 indicates a discrepancy between measured and modeled values. A possible explanation for this discrepancy is that the solar flux in the Herzberg continuum between 200 and
220 nm has been underestimated. A recent measurement of solar irradiance in the stratosphere confirms that the calculated solar flux may indeed be too low. As a result the atmospheric lifetimes of CFCs 11 and 12 would be lowered, which also would reduce the ozone depletion estimate.
The effect of anthropogenic and natural emissions of organic bromine compounds has been considered in the model and found to have a minimal effect on the ozone depletion estimate.
Measurement of C
2
H
2
and C
2
H
2
can be used to infer local concentrations of HO and
Cl, a further check on observed and calculated profiles.
-67-

Table 3 (continued)
Modeling
Based on NASA/WMO 1981 recommended rate constants for reaction of OH with H0
2
,
H0
2
NO
2
, HN0
3
and on recent remeasurements of the UV absorption cross section of
H0
2
NO
2
, the steady state ozone depletion forecast is now 6%. In addition, there is now better agreement between measured and modeled concentration profiles of key stratospheric species.
Latest model results based on the most recent NASA/JPL recommended values for the rate constants (1982) show a further reduction of the steady state ozone depletion estimate to 3.2%. Calculated C10 at 40 km is now in better agreement with the observations. Further improvement in the agreement between theory and observation is possible if the rate constant for the 0 + C10 reaction proves to be slower, but the agreement between the calculated and observed ozone in the upper stratosphere becomes much poorer.
A calculation was performed on the effect of coupling the perturbations to the atmosphere of CFCs together with increased emission rates of CH4, C02, N20, and
NOX. Results show that at 2010 a slight increase of about 1% in total ozone is calculated, whereas with CFCs alone a 2% decrease is calculated.
There is difficulty in reproducing a pronounced spring ozone maximum at high latitudes. This may reflect overestimation of N0
2 latitudes.
by the model as evidenced from comparison with the observed low concentration of N0
2
in winter at high
Detailed calculations of the diurnal variations of stratospheric trace species have been performed. The model-predicted diurnal variations of column densities of C10 above 30 and 40 km are in good agreement with the de Zafra, Solomon, et al., 1984 observations. It is argued that observation of the diurnal behavior of stratospheric C10 can place important constraints on the chemistries of HOC1 and ClON0
2
. This is significant because so far there has been no definitive detection of these last two species.
A new tracer transport scheme has been developed in isentropic coordinates with advective transport driven by diabatic circulation and with eady transport parameterized by a sing le horizontal diffusion coefficient,K yy
. Calculations of the latitudinal and vertical distributi6hs of N
2
O and
-68-

Table 3 (continued)
Modeling
HNO
3
based on this new transport scheme are in good agreement with observation.
Having the validity of the new transport formulation established permitted the full chemical scheme (Including the diurnal code) to be interfaced with the new
2-D model. The calculated distribution of ozone (both seasonal and latitudinal) is in significantly better agreement with observations than with the older version of the AER 2-D model.
The refined new 2-D model has been used for interpreting new field data (e.g.,
BIC data) and for assessing ozone perturbations due to future increases of CFCs and other gases.
The nonlinear response of ozone to stratospheric chlorine perturbations has been investigated using the AER 1- and 2-D models. Various factors contribution to the nonlinear chemistry/perturbations have been identified and assessed.
The amount of stratospheric NO x is among one of the most critical contributing factors. The onset of nonlinear chemistry occurs as the amount of stratospheric
Cl x
approaches that of NO x
.
Slow reactions that might be of importance to stratospheric chemistry have been identified and assessed. They include reactions such as ClON0
2
+ H
2
0  HOC1 +
HNO
3
; N
2
0
5
+ H
2
0  2HNO
3
; HN0
4
+ H
2
0  HN0
3
+ H
2
0
2
; HCI + ClON0
2
- Cl
2
+ HN0
3
; and H
2
0
+ 0
3
 H
2
0
2
+ 0
2
. These reactions could have considerable impact on stratospheric chemistry if their rate constants lie between 1023 and 10 -16 cm -3 molec -I s -1 .
Preliminary 2-D model results show that the calculated amounts of column ozone reduction are in direct proportion to stratospheric chlorine abundances (from 0 to 15 ppb range). These results are in share contrast to 1-D model calculations, which exhibit significant nonlinear response of column ozone to stratospheric chlorine perturbations.
Dr. W. C. WANG ---Atmospheric and Environmental
Research, Inc.---84-518. Possible Climatic Effect of
Atmospheric Trace Gases.
The studies of Wang and Sze (see 83-448) were extended by the use of a 2-D
(altitude-latitude) radiative-dynamical model developed by one of the investigators. Major findings
-69-

Table 3 (continued)
Modeling are: the thermal radiation flux perturbations caused by increase of carbon dioxide that result in climate change are different in nature from those caused by other trace gases; use of the 2-D model yields more realistic temperatures and humidity distributions than does use of the 1-D model; in spite of its limitations, use of the 1-D model leads to surface warming effects when using the moist adiabatic critical lapse rate, which are in close agreement with those obtained by the 2-D model.
Drs. W. C. WANG and N. D. SZE Atmospheric and
Environmental Research, Inc. 83-448. Modeling
Climatic Effects of CFCs and 0
3
(completed).
This work encompassed modeling studies of the effects of CFCs, 0
3
, and other atmospheric trace gases on the temperature at the surface of the earth and at various levels above the surface.
Using a one-dimensional radiative-convective-photochemicaI model developed by the investigators,they addressed direct surface warming effects of CFCs, potential combined effect of CFCs and 0
3
on surface temperature, sensitivity of climatic effects of CFCs and 0
3
to model physical parameterization, and potential combined climatic effects due to emissions of CFCs, C0
2
, N
2
0, CH
4
, NO,, and 0
3
. The investigators found that, for the scenario they used covering the period 1980-2010, C0
2
contributed a surface warming effect of 0.4 K, and an additional surface warming effect of 0.4 K can be attributed roughly equally to the direct radiative effect of NO,,_
CFCs, CH
4
, and N
2
0 and to the indirect radiative effect associated with 0
3 redistribution.
F. Other
Dr. M. J. BAILEY -- University *of Maryland -- 80-317.
Uncertainties and Benefit-Cost Analysis of CFC Control
(completed).
A recently concluded, EPA-funded analysis of the potential costs and benefits of CFC control has been expanded and
-70-
Using the 2-D model and scenarios which they describe, the investigators calculate potential surface warming effects of the various trace gases.

I
Table 3 (continued)
Other further refined. The new study takes into account recent revisions in atmospheric models and projected future changes in atmospheric composition. Although the range of possible outcomes is broad, indications for the most likely case are that the benefits of unregulated fluorocarbon use will outweigh any of their harmful effects.
Drs. D. BERGER and F. URBACH -- Temple University -75-62, 82-414.
Ground-Lev4l Monitoring of Ultraviolet Solar Radiation (completed).
The monitoring of solar ultraviolet radiation, which was initiated by the
Climatic Impact Assessment Program (CIAP) and subsequently funded for one year by
CMA FPP, was then supported by NOAA with EPA funds. It was again funded by CMA
FPP for the period January 1 - June 30, 1983.
Dr. F. 0. CLARK University of Kentucky at Lexington -- 84-530.
Collection and Analysis of Stellar Photometry Data.
This project entails collection of world-wide stellar photometry data, which will be used to correct past and future Umkehr ozone data for aerosol effects. At present, solar transmission data taken at Mauna Loa, Hawaii, are assumed to be representative world-wide and are applied to the measurements taken from other stations in the network.
A feasibility study was Carried out under a NOAA subcontract (see 83-466), to determine ;Whether sufficient data sets were available. Data have been collected from over 14 astronomical observatories, which span a latitude range of 37rS -to
6O 0 N. Lengths of these data sets vary from 1-31 years. The data are being processed in a form suitable for use in correcting unknown data for aerosol effects.
Dr. J. J. DeLUISI -- National Oceanic and Atmospheric
Administration, Boulder -- 83-466. Umkehr Aerosol Corrections.
This project entails collection of world-wide solar transmission and lidar measurements, which will be assimilated into a data set for the purpose of correcting past and future Umkehr ozone data for aerosol effects. At present, solar transmission data taken at Mauna Kea, Hawaii, are assumed to be
-71-

Table 3 (continued)
Other representative of the global scale and are applied to the measurements taken from other stations in the world-wide network.
Dr. Frank Clark was given a subcontract to determine whether there were sufficient stellar photometry data sets available in order to derive the latitudinal and temporal variations of the solar transmission data. He has been able to locate many observatories that have made stellar photometry measurements continuously. Collection and analysis of these data sets are being carried out through a contract between Dr. Clark and CMA (see 84-530).
Because there were difficulties in obtaining personnel to perform any additional aspects of this work (over and above stellar photometry), the contract was terminated by mutual consent.
Drs. E. PARZEN and M. PAGANO -- Frontier Science and Technology Research
Foundation, Inc. -- 76-106. Total World Ozone Level: Statistical Analysis
(completed).
Ozone column measurements from at least 20 stations have been evaluated statistically to detect trends in recorded ozone concentrations and to establish the limits of detection for such trends. Time series analysis has been shown to be substantially more sensitive in detecting non-random ozone changes than the estimates of such sensitivity made by the Federal Task Force on Inadvertent Modifications of the Stratosphere (IMOS) in 1975. Analysis of ozone data from 9 stations shows that no detectable abnormal trend in the ozone data has occurred over the period 1970-75. The absence of detectable trends provides an upper limit for actual depletion and a test of model predictions.
If sufficient sensitivity is achieved, this technique will enable an effective early warning system for ozone depletion to be established.
Dr. J. A. PYLE -- Rutherford Appleton Laboratory, England -- 83-456,
84-511. Diurnal Variations by Comparisons of Field Data and Calculations.
The 2-D model developed at Oxford University has been updated and transferred to the Rutherford Appleton Laboratory. It is being used to study diurnal variations of stratospheric

Table 3 (continued)
Other species by detailed comparison of field data (from balloon and satellite instruments) and numerical model calculations.
Drs. G. C. TIAO and G. REINSEL--University of Chicago
(formerly University of Wisconsin); University of Wisconsin -- 78-250,
80-304, 81-374, 83-462. Statistical Analysis of World-wide Stratospheric
Ozone Data for the Detection of Trend.
Ground-based and satellite total column ozone and profile ozone data have been analyzed using statistical time series analysis. For the fourteen-year period
1970-1983, the average change in total ozone based on 36 Dobson stations is
(-0.17 ± 1.10)%/decade. The error limits are 95% confidence limits. The analysis takes into account instrumental shifts and solar variability. The change is not statistically significant.
In an analysis of Umkehr ozone profile data through 1981 from 13 Dobson stations, changes of -3.2 ± 3.30%/decade in layer 9 (43-48 km -3.2 ±
1.7%/decade in layer 8 (38-43Km), -2.6 ± 1.7 %/decade in layer 7(34-38 km),
+0.3 ± 1.6%/ decade in layer 6 (29-34 km), and -0.3 ± 1.6%/decade in layer 5 (24-29 km) are estimated. Corrections for aerosol volcanic effects using Mauna Loa, Hawaii, atmospheric transmission data, for instrument problems, and for solar activity are included in the trend models. The trends in layers 7 and 8 are statistically significant. Layers 1-5 have also been analyzed, with a statistically significant change of +8.7 ± 7.6%/decade seen in layer 1 (5-10 km). The estimated changes in the Umkehr profile are not inconsistent with chemical model calculations for coupled perturbation effects.
A preliminary analysis of balloon ozone sonde data has been made for trends in the region below 33 km during the period 1970-1982 at 13 stations. In the 15-20 km region, significant changes of -6.9 ± 3.0%/decade in layer 3A and -5.0 ±
3.4%/decade in layer 3B are not consistent with chemical model calculations, which show little or no change. A significant positive change of +8.3 8.2% decade was-found for layer 1A and +6.7 ± 5.6%/ decade for-layer 1B, as was the case with Umkehr data. The impact of instrumental problems on the trend estimates is being investigated.
The first four years of Nimbus 7 satellite ozone data (1978-82) have been analyzed. Results for this limited period of time show significant positive trends in layers 5
-73-

Table 3 (continued)
Other and 6 and significant negative trends in layers 9 and 10. The satellite data also indicate that there is good global representation with the Umkehr network for this period. Earlier studies with Nimbus 4 satellite data (1970-1977) show good global representation over the period for both the 13 station Umkehr network and the 36 station Dobson total ozone network used in the trend studies.
Ozone changes associated with solar effects are observed to be a factor of two to four less than those calculated by the chemical models for the upper proftle
(layers 5-9) and the total column.
Dr. G. S. WATSON -- Princeton University -- 78-257, 81-360;
Drs. G..S. WATSON and G. W. OEHLERT -Princeton University -- 82-409,
83-477. St-atistical Investigations of the CFM Problem.
Total column ozone data through 1982 from 36 Dobson stations are analyzed for trends. After correction is made for instrument shifts and solar variability, the trend is (-0.59 ± 1.16)%/decade. The estimate is not statistically significant. one possible interpretation for the change in sign upon inclusion of the solar flux variation is that ozone has increased during 1970-1981 but not as much as the solar curve would predict.
An alternative method has been developed for examining the Umkehr data for trends in the ozone profile. This scheme uses noninverted N values from the
Umkehr observations and determines changes in the shape of these values as a function of solar zenith angle. The analysis has been carried out using the linear part of the N values curve. Use of a hockey stick CFC depletion curve and a proxy (atmospheric transmittance) for atmospheric aerosols indicates that the estimated change is -9.2% at 40 km for the period 1970-1980. The result is not statistically significant.
The data base of 1957-1979 atmospheric temperatures (radiosondes) covering the pressure range of 30 to 850 mb has been examined. The objective was to see if stratospheric cooling was occurring as predicted from the C0
2
build-up. The analysis shows that a relative change in the temperature profile of the atmosphere is occurring with approximately the shape predicted by the atmospheric models. The analysis
-74-

Table 3 (continued)
Other shows a cooling pattern above and a warming pattern below 12 km.
Dr. S. ZEGER -- Johns Hopkins University -- 83-460.
Dose Response of Nonmelanoma Skin Cancer to UV Light.
The purpose of this study is to validate current estimates of dose-response relationship between ultra-violet light and non-melanoma skin cancer.
The available literature on the relationship between nonmelanoma skin cancer
(NMSC) and ultraviolet radiation (UV) has been summarized. The study provides an overview of the subject together with detailed listings of papers on epidemiological studies and laboratory animal studies. Furthermore, it provides a statistical critique of the 1981 epidemiological study by Scotto, et al.
Among the major findings
1) Clear and conclusive evidence that the incidence rate for NMSC increases with increasing exposure to UV.
2) Several potentially important variables have not yet been included in estimates of the biological amplification factor, which relates NMSC incidence rate to increase in UV intensity. In particular, those estimates that are based on the assumption o reciprocity are not suitable for analyzing data from epidemiological studies.
3) Squamous cell NMSCs have a stronger UV dependence than the more prevalent basal cells.
The report also identifies major issues needing further scientific cETn-sideration.
G. Consultants
Dr. J. G. Anderson Harvard
University
Stratospheric
Measurements
Dr. A. W. Castleman, Jr.
Dr. F. 0. Clark
Dr. W. C. Gardiner, Jr.
Dr. W. L. Gates
Pennsylvania
State University
University of
Kentucky
University of
Texas
Oregon State
University
Heterogeneous
Chemistry
Millimeter
Wavelength
Spectroscopy
Chemical
Kinetics
Effects:
Climate
Dr. D. R. Herschbach
Dr. W. Klemperer
Dr. J. E. Lovelock
Dr. D. G. Murcray
Dr. J. H. Shaw
Dr. L. E. Snyder
Dr. P. H. Stone
Harvard
University
Harvard
University
Private
University of
Denver
Ohio State
University
University of
Illinois
Massachusetts-
Institute of
Homogeneous
Chemistry
Kinetics, and
Spectroscopy
Kinetics and
Atmospheric
Spectra
Atmospheric
Measurements
Stratospheric
Measurements
Atmospheric
Spectra
Millimeter
Wavelength
Spectroscopy
Effects:
Climate

Dr. F. Urbach
Dr. R. T. Watson
Technology
Temple
University
NASA
-76-
Effects:
Human
Chemical
Kinetics and
Photochemistry
June 1, 1985

Table 4A
Research Funded by the Chlorofluorocarbon Industry and
Administered by the Chemical Manufacturers Association
WORK COMPLETED*
Programe Investigator
Investigation of spectroscopy of and photochemical changes in fluorocarbons
Monitoring of fluorocarbons in the atmosphere and simulation of atmospheric reactions of flurocarbons b
Sandorfy
Taylor
Measurement of fluorocarbons in Lovelock the atmosphere b
Laboratory investigation of the Stedman feasibility of measuring C10 in the atmosphere by the chemical conversion-resonance fluorescence detection method
Organization a
U. of Montreal
U. of california, riverside
U. of Reading
U. of Michigan
Proposal
Number
73-2
73-3
73-1
74-7
Completion
Date
10/11/74
10/16/74
10/27/74
2/28/75
Laboratory determination of sensitivity of laser-induced fluorescence for the detection of C10 under atmospheric
Conditions
Davis
Pitts Continuation of 73-3 b
Continuation of 73-l b
Investigation of ion-molecule reactions involving chloro-
Lovelock
Mohnen
U. of Maryland
U. of California,
Riverside
U. of Reading
SUNY-Albany
74-10
74-2
74-3
75-64
5/31/75
12/31/75
12/31/75
4/1/76 fluorocarbons
Development of an instrument to measure 0, C101 0
3 strastosphere b
, and
Young Xonics, Inc. 75-50 4/7/76
(continued)
___________________________
*Copies of final reports are available upon request to Fluorocarbon Program Manager,
Chemical Manufacturers Association, 2501 M Street, NW, Washing-ton, DC 20037.
-77-

Program
Table 4A (continued)
Investigator Organization a
Washington State U.
Proposal
Number
75-2 Measurement of fluorocarbons and related chlorocarbons in the stratosphere and upper troposphere b
Continuation of 74-2
Rasmussen
Pitts U. of California,
Riverside
Washington State U.
75-12
75-53 Investigation of the destruction of chlorofluormethanes by naturally occurring ions
Ground-based millimeter wavelength observations of stratospheric C10
Laboratory and theoretical studies of the ultraviolet and visible electronic spectra of CI0 b
Modeling of the fluorocarbon- Ozone system b
Critique of models used toestimate chlorofluorocarbon effects on ozone b
Studies of reactions of H0
2 by laser magnetic resonance
Continuation of 75-50
Measurement of stratospheric distribution of fluorocarbons and related species by infrared absorption spectroscopy b
Measurement of reaction rates relevant to the fluorocarbon-ozone problem 2
Measurement of OH in the stratosphere by laser induced fluorescence
Campbell
Ekstrom
Nicholas
Sze
Cunnold,
Alyea,
Prinn
Thrush
Young
Murcray
Birks
Davis
Battelle Northwest
York U.
ERT, Inc.
CAP Associates
U. of Cambridge
Xonics, Inc.
U. of Denver
U. of Illinois
U. of Maryland
75-27
75-11
75-32
75-24
75-58
75-86
75-13
75-1
75-87
-78-
Completion
Date
4/15/76
4/15/76
4/23/76
5/24/76
6/14/76 0
8/18/76
9/10/76
11/8/76
11/15/76
1/24/77
2/4/77
2/23/77
(continued)

Table 4A (continued)
Program
Exploration for unidentified factors in the fluorocarbon ozone problem b
Laboratory studies of the infrared vibration-rotation spectrum of C10
Absolute calibration of fluoro-carbon measurements
Collection and analysis of
Antarctic ice cores
The electron capture detectors a reference standard in the analysis of atmospheric halocarbons
Laboratory measurement of climatic effects of fluoro-carbons b
Investigator Organization a Proposal
Lovelock
Nicholls
Stedman
Rasmussen
Lovelock
Davis spectroscopic absorption cross sections of CIO
Measurement of fluorocarbon content of "antique" air samples
Rasmussen
Measurement of HC1 and HF in Buijs the stratosphere by Fourier transform spectroscopy b
Berger Continuation of program for
Ground level monitoring of ultraviolet solar radiation b
Birks Continuation of 75-1 b
Studies of heterogeneous reactions b
Meteorological and multi-
Diensional modeling considerations relating to atmospheric effcts of halocarbons b
Birks
Cunnold,
Alyea,Prinn
Cunnold,
Alyea,Prinn
Private
York U.
U. of
Michigarr
Rasmussen
Assoc.
Private
U. of
Maryland.
Washington
State U. 75-71
Bomem, Inc.
Temple U.
75-98
Completion
Date
3/10/77
9/26/77
U. of Illinois 76-117B 12/12/77
Number
75-67
75-30b
76-132
75-84
76-120
75-73
9/2/77
75-62
U. of Illinois 76-117A 12/12/77
CAP Associates 76-122 12/12/77
CAP Associates 76-122S
3/25/77
4/1/77
4/19/77
5/3/77
5/12/77
10/20/77
12/12/77
(continued)
-79-

Program
Table 4A (continued)
Investigator Organization a Proposal
Number
Electron spin resonance detection of stratospheric radicals
Measurement of the concentration of methyl chloride in air in Kenya
Continuation of 75-6 7b
Kilauea volcanic emissions--halocarbon measurement
Laboratory determination of the feasibility of laser magnetic resonance for C10 detection and reaction studies
Photochemical and chemical
Kinetic measurements of stratospheric importance with respect to the fluorocarbon issue b
Laboratory measurement of high resolution infrared spectra of chlorinecontaining molecules of stratospheric interest b
Reactions of the H0
2
radical studied by laser magnetic resonance
Construction of Fourier transform spectrometer
Interlaboratory comparisons of fluorocarbon measurements b
Generation and exchange of calibrated samples of fluorocarbons
Laboratory investigation of the heterogeneous interaction of CI and CIO ith H
2
SO4 b
Ehhalt
Rasmussen
Lovelock
Rasmussen
Howard
Timmons
Muurcray
Thrush
Buijs
Rasmussen
Stedman
Martin
Nuclear Research
Establishment
Private
Private
Oregon Graduate
Centre
NOAA-Boulder
Catholic U.
Bomem,Inc.
Private
U. of Michigan
Aerospace Corp.
-80-
76-145
77-181
77-144
77-215
75-47
76-129
75-90
76-142
77-151
75-81
Completion
Date
12/12/77
12/12/77
12/23/77
12/27/77
1/10/78
1/16/78
3/8/78
3-8-78
3/10/78
3/27/78
(continued)

Program
Continuation of 75-32 b
Studies of compounds of sulfur,oxygen, and chlorine b
Total world ozone level: statistical analysis
Table 4A (continued)
Investigator
Sze
Kaufman
Organization
ERT, Inc.
Emory U. a
Proposal
Number
76-115
76-126
Completion
Date
3/28/78
5/24/78
Parzen,
Pagano
Frontier
Scienceand
Technology
Research
76-106
Foundation,
Inc.
U. of Denver 76-135
5/25/78
Stratospheric measurement ofCIO and OH
Laboratory study of the UV and spectra of HOCI, HOONO
2
And HCIO
4
in the temperature range of the stratosphere
Photochemistry of small chlorinated molecules b
Continuation of 75-2
Murcray
Knauth
Wiesenfeld
U. of Kiel
Cornell U.
77-171
76-128
5/30/78
6/14/78
7/5/78
Atmospheric chemistry of
Continuation of 75-81
Program operation of stations at
Rasmussen
Pitts
Martin
Investigator
Lovelock,
Washington
State U.
U. of
75-59
77-190
8/10/78
11/13/78
California,
Riverside
Aerospace
Corp.
75-81 11 12/6/78
U. of Liege 76-141 12/11/78 Ground-based infrared measurements b
Measurements of HCI,HF,CIO, e.c.t., in the stratosphere high resolution infrared spectroscopy
Zander
Girard ONERA-France 75-88
Coordination and analysis of
Data for atmospheric lifetime experiment b
Instrument of fluorocarbons and related chlorocarbons
Cunnold,
Ridley
CAP
Associates
York U. the stratosphere by collection and analysis
Continuation of 76-122 b Cunnold,
Alyea,
Prinn
CAP
Associates
_81-
(continued)
Table 4A (continued)
77-213
76-102
77-199
Organization
Private a
Proposal
Number
77-193
1/2/79
2/13/79
2/26/79
2/26/79
Completion
Date
2/28/79

Adrigole and Barbados for atmospheric lifetime experimet b
Operation of stations in
American Samoa and Tasmania
Development of primary fluorocarbon standards
Experimental investigation of the ranching ratio in the
OOD)+ H
2
0
Acquisition of on-board digital recording system
Theoretical models of stratospheric chemistry, per turbations, and trace gas measurement b
Determination of the photo-diassociation process and absorption cross section ofFC-11 and 12 in the near
UV.
Continuation of 76-129b
Total chlorine measurements in the troposphere and stratosphere millimeter wave observations of chlorofluoromethane byproducts in the stratosphere b
Continuation of 76-126
Photoabsorption cross section for compounds of atmospheric interest.
-82-
Rasmussen
Lovelock
Zellner
Murcray
Sze
Stuhl
Timmons
Eggleton
Solomon, deZafra
Kaufman
Takacs
(continued)
Oregon
Graduate
Center
Private
U. of
Goettingen
SUNY Stony
Brook
77-201
78-226
77-195
U. of Denver 77-211
AER, Inc. 77-173
U. of Bochum 77-170
U. of Texas, 77-214
AERE Harwell 76-116
Emory U.
Rochester
Inst.
Technol.
76-130
77-197
77-196
3/29/79
4/2/79
4/12/79
4/12/79
4/17/79
5/3/79
6/15/79
7/6/79
7/6/79
7/6/79
7/24/79

Table 4A (continued)
Program Investigator Organization a
Proposal
Number
Completion
Date
7/30/79 Lower stratospheric measurement of non-methane hydrocarbons
Laboratory study for determination of the equilibrium constant of the reaction CL0
2
+H
2
0=HOCI and the UV spectrum of
HOCI
Effect of aerosol scattering on ozone measurements with the
Dobson spectrophotometer
Continuation of 75-92 b
Ladies of reactions of importance in the stratosphere b
Photodegradation of chlorofluoromethanes in the troposphere
Follow-up for photodecomposition of chloromethanes absorbed in silica surfaces b
Continuation of 77-213b
Rasmussen
Knauth
Moe
Murcray
Birks
Korte
Ausloos
Private
U. of Kiel
Private
U. of Denver 77-152
U. of
Colorado
U. of Munich 77-194
NBS
76-140
77-224
78-235
77-192
77-186
Continuation of 77-199b
Continuation of 76-128 measurement of halogen compounds for determination of total chlorine and total fluorine in the stratosphere.Lng.long-path interferoric spectroscopy
-83
Cunnold,
Alyea,
CAP
Associates
Prinn
Cunnold,
Alyea,
Prinn
CAP
Associates
Wiesenfeld Cornell
Buijs Bomem, Inc.
(continued)
78-251
78-252
77-220
77-168
8/9/79
9/12/79
10/17/79
11/8/79
11/16/79
11/28/79
12/17/79
1/18/80
2/1/80
2/4/80

Program
Determination of measurement system for the determination of total chlorine in air
Indentification of FC 21 in the atmosphere
Continuation of 76-130
Continuation of 77-193 b b
Table 4A (continued)
Investigator Organization a Proposal
Number
Skogerboe Colorado
State U.
77-206
Rasmussen
Solomon, deZafra
Oregon
Graduate centre
SUNY Stony
Brook
Private
78-260
77-225
78-243
Continuation of 77-192 b
Lovelock,
Simmonds
Birks
Howard
U. of
Colorado
78-244
NOAA-Boulder 76-100 Laser magnetic resonance study of HO
2
chemistry
Study of Clo chemistry by laser magnetic resonance
Continuation of 77-201 b
Howard
Rasmussen
NOAA-Boulder 77-223
78-248
Sze
Oregon
Graduate
Center
AER, Inc. 78-234 Development and implementation of a simplified multidimension model for stratospheric chemistry perturbations, radiation feedback and trace gas measurement b
Continuation of 77-142 Rasmussen
Murcray
Oregon
Graduate
Center
78-247
U. of Denver 78-228 Detection of selected molecules by ground-based solar spectroscopy
Analysis of Release of
FC-11 from Rigid Plastic
Foam Products in the U.S.
Effectiveness of various untreated sand surfaces bringing about the oxidation of CCI
4 and CF
2
CI
2
, CFCI
3
,,
Shamel
Ausloos
A. D.
Little, Inc.
NBS
79-275
78-254
84-
Completion
Date
2/4/80
2/5/80
2/13/80
2/18/80
2/20/80
3/12/80
3/12/80
4/24/80
5/14/80
5/28/80
5/29/80
5/29/80
6/6/80
(continued)

Program
Table 4A (continued)
Investigator Organization
The exponential dilutionchamber for the calibration of instruments and the preparation of standards b
Rates of reaction of Cl atoms with the primary products of alkane phtooxidation
Determination of FC-21 and other halocarbons in
Lovelock
Kurylo
Bruner the troposphere
Determination of atomic oxygen yields I the phtolysis of OCL and CIOO
Phillips
Continuation of 78-243 b Simmonds
Continuation of 78-248 b Rasmussen
Private
NBS
Urbino U. a
U. of Canterbury
(N.Z.)
Private
Proposal
Number
78-264
78-233
78-256
78-241
79-280
Orego-Graduate
Center
Oregon Graduate
Center
79-279
78-263
CAP Associates 79-281
Completion
Date
7/9/80
9/4/80
9/23/80
9/30/80
12/22/80
12/29/80
1/5/81
1/5/81
Operation of Fifth ALE Rasmussen
Station, Cape Meares, OR b
Combination and Cunnold, continuation of 78-251 and 78-252 b
The A2
Л
<- X 2 Л
I system If CL0 b
Band
Alyea,
Prinn
Coxon
Statistical analysis of world stratospheric ozone data for the detection of
Tiao,
Reinsel trends b
Continuation of 78-244 b Birks
Dalhousie U.
U. of Wisconsin
U. of
Colorado
78-255
78-250
79-276
1/22/81
1/26/81
-85-
1/27/81
(Continued)

Program
Determination of tropospheric halcarbons and their relative
Table 4A (continued)
Investigator
Simmonds,
Lovelock importance
Laboratory measurement of
Infrared spectra of selected stable molecules
Buijs
Organization
Private
Bomem, Inc. a
Continuation of 77-225 b
Continuation of 75-11
Continuation of 78-234 b
Solomon, deZafra
Nicholls
Sze
York U.
AER, Inc.
Proposal
Number
79-269
77-221
Completion
Date
3/10/81
3/11/81
SUNY Stony Brook 79-278 4/6/81
75-11 11 4/27/81
79-273 5/28/81
Continuation of 78-264
Simultaneous balloon flight with J G Anderson
F-22 measurements in the
Atmosphere
Uncertainties and benefit
Cost analysis of CFC control
Statistical investigations of the CFM problem b
Continuation of 77-152 b
Continuation of 79-281 b
Lovelock
Murcray
Rasmussen
Bailey
Watson
Murcray
Cunnold,
Alyea,
Prinn
Simmonds
Private
U. of Denver
Private
U. of Maryland
Princeton U.
U. of Denver
CAP Associates
Private
80-293
77-166
80-308
80-317
78-257
78-265
80-323
80-324
5/29/81
6/8/81
6/8/81
10/20/81
10/21/81
10/30/81
11/23/81
1/27/82 Continuation of 79-280 b
Operational costs for flights planned in 1977
Continuation of 79-273 b
Continuation of 8G-325
Buijs
Sze
Rasmussen
Bomen, Inc.
AER, Inc.
Oregon Graduate
Center
77-156
80-311
81-376
3/22/82
4/20/82
4/20/82
(Continued)
-86-

Program
Continuation of Part of
80-323
An intercomparison of measurement of stratospheric
Continuation of 79-278 b
Continuation of 78-263 and
79-279
Joint Calibration Study of
F-21
Sling of the CFC effect on the ozone layer b
Development of technique for measuring total chlorine content of air
Absorption measurements of
HOCI and related molecules
Continuation of 79-276 b
Continuation of 79-276 b
Measurement of the Vertical
Distribution of HCI, O
3
HCHO and ratio HF/HCI
, and
An infrared laboratory spectroscopy of halogen containing molecules b
Continuation of 78-250
Millimeter Measurements and spectral Predictions b
Table 4A (continued)
Investigator
Rosen
Murcray,
Solomon, deZafra
Rasmussen
Bruner
Brasseur
Howard,
Birks
Fehsenfeld
Timmons
Birks
Birks
Jouve
Traub,
Chance
Reinsel,
Tiao
Lovas,
Suenram
Organization a
ERT, Inc.
U. of Denver, 80-328
SUNY Stony-
Brook
Oregon
Graduate
Center
Urbino U.
Institut d'Aeronomie
NOALA-Boulder/
U. of Colorado
U. of Texas,
Arlington
U. of Colorado 80-321
U. of Colorado 80-329
U. of Reims
Smithsonian
Astrophysical
Observatory at
Harvard
U. of
Winsconsin
NBS
Proposal
Number
81-377
80-316
80-325
81-365
80-320
77-222
78-258
79-290
80-318
80-304
81-350
Completion
Date
4/26/82
6/1/82
6/2/82'
6/2/82
6/2/82
6/3/82
6/15/82
6/15/82
6/28/82
6/28/82
7/30/82
8/20/82
10/26/82
11/18/82
(continued)
-87-

Program
Continuation of 80-323
Continuation of 80-324
From HOCI Photolysis b b
Yield of Atomic Oxygen
Continuation of 76-137
Table 4A (continued)
Investigator
Cunnold,
Alyea,
Prinn
Simmonds
Organization a
CAP Inc.
Private
Phillips
Bonetti
Carli
Kurylo
Proposal
Number
81-361
U. of Canter- bury (N.Z.)
81-342
U. of
Florence,
CNR-IROZ
NBS
81-370
80-297
80-307
Completion
Date
12/03/82
12/21/82
12/29/82
2/7/83
2/14/83 Reactions within the HO
X
Cycle
Joint Calibration Study of
F-21
Near- and Far-Infrared
Spectroscopy
Comparison of Umkehr
And microwave Ozone
Profiles
Atmospheric Monitoring of
F-21
IR Laser Investigation of
Halogen species
Laboratory Studies of
Stratospheric Reactions b
Continuation of 80-316 b
Continuation of 75-13
Continuation of 78-255
Continuation of 78-257 b
Continuation of 80-311 b
Rasmussen
Saykally
Duetsch
Kuenzi
Bruner
Burrows,
Cox
AERE, Harwell 80-334 5/24/83
Ravishankara Georgia Tech. 81-368 5/24/83
Solomon, deZafra
Murcray
Coxon
Watson
Sze
Oregon
Graduate
U. of
California,
Berkeley
ETH, U. of
Bern
Urbino U.
SUNY Stony
Brook
AER, Inc.
81-356
80-300
81-371
80-330
81-362
U. of Denver 76-101
Dalhousie U. 80-315
Princeton U. 81-360
81-366
2/22/83 41
5/12/83
5/13/83
5/24/83
6/22/83
6/24/83
7/18/83
7/26/83
8/16/83
(continued)
-88-

Table 4A (continued)
Program
Continuation of 81-366 b collaborative studies on atmospheric spectroscopy b
Continuation of 75-62
Reaction of Clo with OH
Investigator
Sze
Goldman,
Barbe
Urbach organization a
AER, Inc.
U. of Denver,
U. of Reims
Temple U.
Proposal
Number
82-405
80-322
82-414
Completion
Date
8/16/83
8/23/83
8/23/83
Reaction of OH with C10
Quantitative Infrared line strengths for.0
2 b
Equilibrium Constant for
OCCOO Formation
Continuation of 80-118 b
Donovan U. of
Edinburgh
79-286 9/9/83
Ravishankara Georgia Tech. 80-295 9/12/83
Zahniser,
Kolb
Zellner
Aerodyne
Research,Inc.
U. of
Goettingen
81-355
80-331
9/13/83
10/28/83
Continuation of 76-141 b
Continuation of 78-265 b
Continuation of 80-321,
80-329
Continuation of 81-361 b
Airborne Killimeter Wave
Determination of CIO
Reactions Of H0
2
Radicals b continuation of 80-320 b
Traub,
Chance
Zander
Murcray
Birks,
Sievers
Cunnold,
Alyea,
Prinn
Beckman
Thrush
Brasseur
Smithsonian
Astrophysical
Laboratory
At Harvard
U. of Liege
81-375
78-232
U. of Denver
CAP, Inc.
Queen Mary
College,
London
U. of
Cambridge
Institut d'Aeronomie
Spatiale
-89-
Table 4A (continued)
Program
Kitt Peak Observations with
Balloon Intercomparison
Investigator
Stokes
Organization a
Battelle
Northwest
81-364
U. of Colorado 81-358
82-422
79-282
81-378
82-396
10/28/83
11/7/83
11/7/83
4/13/84
4/13/84
(continued)
Proposal
Number
82-397
1/20/84
1/20/84
3/15/84
Completion
Date
4/30/84

Campaign
Chemistry of Halogen
Species Using IR Diode
Laser Spectroscopy
Continuation of 81-360 b
ALE Participation
Continuation of 81-370
Continuation of 80-304C
Cox
Watson,
Oehlert
Fraser
Simmonds
Reinsel,
Tiao
Howard
AERE
Harwell
82-400 5/29/84
Princeton U. 82-409 5/29/84
CSIRO 82-415
Private 82-421
U. of
Wisconsin
81-374
NOAA-Boulder 79-289
5/29/84
5/29/84
7/3/84
7/17/84 Kinetic Studies of stratospheric chlorine chemistry
Gas Phase Reaction of
NaOH with HCI b
Continuation of 81-362
Continuation of 81-375
c c
Silver,
Zahniser,
Kolb
Solomon, deZafra
Traub,
Chance
Aerodyne
Research
Inc.
82-401
SUNY Stony
Brook
Smithsonian
Astrophysical
Laboratory at
82-410
82-445
Harvard
U. of Denver 82-413
8/15/84
9/22/84
9/26/84
10/23/84 Publication of High
Resolution Laboratory
Spectra
Laboratory Spectroscopic
Studies of stratospheric
Gases
Continuation of 81-364
Identification of
Photodissociation Products by REMPI
Murcray
Ballard
Murcray
Steimle
RAL
U. of Denver
U. of Oregon
82-444
82-423
82-418
12/10/84
12/27/84
3/4/85
Continued
-90-

Table 4A (continued)
Program
Modeling Climatic Effects of CFCs and CO
3
Balloon Intercomparison
Campaign
Pressure and Temperature
Dependence of HO+ HO
2
NO
2
Automation of Dobson
Spectrophotometer for
Umkehr Measurements
Photoabsorption Cross
Section of 0
2
in the 192-
204nm
Continuation of 81-358 c
Latitudinal Variations-of several compounds b
Balloon Intercomparison campaign
Continuation of 81-368 c
Investigator
Wang,
Sze
Ogawa,
Iwagami
Becker
Komhyr,
Grass,
Evans,Chopra
Freeeman,
Yoshino,
Parkinson
Birks
Murcray
Zander
Organization
AER, Inc.
U. of Tokyo
U. of
Wuppertal
NOAA-Boulder, 81-363
U. of Colorado
Harvard U. a
U. of Colorado 82-425
U. of Denver
U. of Liege
Proposal
Number
83-448
82-391
83-455
82-412
81-380
82-395
Ravishankara Georgia Tech. 83-449
Completion
Date
4/4/85
4/5/85
4/5/85
4/30/85
4/30/85
4/30/85 c c c a. Abbreviated affiliations are expanded under study descriptions in Table 3. b. Work continued in a follow-on contract.
Final report accepted by the Panel.
June 1, 1985
-91-

Table 4B
Research Funded by the Chlorofluorocarbon Industry and
Administered by the Chemical Manufacturers Association
WORK IN PROGRESS
Program
Consulting for Atmospheric
Life Experiment
Infrared spectroscopy of atmospheric species
Balloon Intercomparison
Campaign
Investigator
Lovelock
Howard
Bonetti,
Carli
Pommereau.
D'Aeronomie organization a
Private
NOAA-Boulder- 80-1299
U. of
Florence,
CNR-IROE
Service
Proposal
Number
81-348
82-389
82-392 Balloon Intercomparison capaign
Balloon Intercomparison
Capaign d
Balloon Intercomparison campaign d
Taylor,
Roscoe oxford U.
NPL
82-393
82-394 Woods,
Pollitt,
Bangham,
Bradsell,
Moss,
Swann
Woods- NPL 82-403 Balloon Intercomparison
Campaign: Master Contract
CFC 11 Release Rate from
Rigid Polyurethane Foams
Rasmussen
Kurylo'
Laufer
Oregon
Graduate
Centre
NBS
82-416
82-402 Kinetic Measurements of
Atmospheric Constituents
Resonance Fluorescence
Measurement of CIO and
Related Species Using
Reel-Down Technique
Anderson Harvard U. 82-429
Contract
Date
Contract
Period
6/17/81 open
-6/4/82 12 mo.
b
6/24/82 20 mo.
b
6/24/82 20 mo.
b
6/24/82 20 mo.
b
6/24/82 20 mo.
b
6/24/82 20mo.
b
10/22/82 12 mo.
b
10/22/82 12 mo.
b
1/27/R3 7 mo.
b
(Continued)
-92-
Table 4B (continued)
Program
Continuation of 79-289
Detection of
Stratospheric OH,HO
2
, and
Investigator
Howard
Anderson
Organization a
NOAA-Boulder 82-424
Harvard
Proposal
Number
82-428
Contract
Date
2/19/83
2/23/83
Contract
Period
12 mo.
b
7 mo.
b

H
2
0 by Copper Vapor Laser
Continuation of 82-391 Ogawa,
Iwagami
Zander
U. of Tokyo 82-438 3/1/83 15 mo.
b
Interpretation of Kitt
Peak Spectra c
Review of Kitt Peak
Data Archives for Iq 4 and other species
Continuation of 82-403
Continuation of 82-394 e
Continuation of 82-393 e
Stokes
Woods
Woods
U. of Liege
Battelle
Northwest
NPL
NPL
82-439
82-417
82-432
82-433
4/5/83
4/12/83
5/9/83
5/9/83
14 mo.
b
15 mo.
b
15 mo.
b
15 mo.
b
Taylor,
Roscoe
Zander oxford U. 82-434 5/9/83 15 mo.
b
Continuation of 82-395 e
Continuation of 82-392 e
Continuation of 82-38g e
Pommereau
Bonetti,
Carli
U. of Liege
Service d'Aeronomie
U. of
Forence
CNR-IROE
RAL
82-435
82-436
82-437
5/9/83
5/9/83
5/9/83
15 mo.
b
15 mo.
b
15 mo.
b
Dilirnal Variations by
Comparisons of Field Data and Calculations c
Continuation of 81-374
Pyle
Reinsel, U. of
Wisconsin,
Tiao
U.of Chicago
AER, Inc.
83-456
83-462
8/9/83
8/22/83
15 mo.
b
18 mo.
b
Continuation of 82-405 C
-D Dimensional Radiative
Convective Model of the
Atmosphere
Sze
Kinoshita Mitsubishi
Res.Inst.
83-465
83-461
9/29/83 12 mo.
b
12/23/83 12 mo.
b
(continued)
-93-

Program
Continuation of 80-322
Continuation of 81-355
Product Determination of
Atmospheric Reactions
Continuation of 82-409
Continuation of 82-422
Balloon Measurements with
Pressure Modulators and
Selective Absorbers c
Continuation of 81-380
Continuation of 82-425
Continuation of 82-396 C
Investigator
Goldman,
Barbe
Zahniser
Lee
Table 4B (continued)
Murcray
Birks
Brasseur
Laboratory Study of
C10 + 0
Temperature Dependence of
The IR Bond Strengths for
F-11 and F- 12
Zellner
Elkins
Laboratory Measurements of
Rotational and Vibrational et ale
Spectra
Trombetti,
Dose response of
Non-Melanoma Skin Cancer to UV light
Halogen Species Chemistry
By IR and UV Spectrocopy
Zeger
Cox
Umkehr Aerosol Corrections DeLuisi
Organization a
NBS
17. of
Bologna and other Italian
Institutions
Proposal
Date
Contract
Date
Contract
Period
2/29/84 12 mo.
b U. of Denver,
U.of Reims
Aerodyne
83-457
83-469
Research,
Inc.
Tsing-Hua U. 83-480
Watson,
Oehlert
Cunnold,
Alyea, Prinn
Taylor,
Roscoe
Princeton U. 83-477
CAP, Inc. oxford U.
83-476
83-484
U. of Denver 84-497
U. of
Colorado
Institute d'Aeronomie
Spatiale
U. of
Goettingen
83-490
83-468
83-478
83-473
83-472
Johns Hopkins 83-460
AERE, Harwell 83-483
NOAA-Boulder 83-466
3/8/84
3/14/84
3/15/84 12 mo.
b
3/26/84 12 mo.
b
4/4/84
4/5/84
4/9/84
12 mo.
24 mo.
b
b
12 mo.
b
6 mo.
b
8 mo.
b
4/11/84 12 mo.
b
4/16/84 17 mo.
5/10/84 12 mo.
b
5/29/84 12 mo.
b
5/30/84 12 mo.
b
6/6/84
6/8/84
12 mo.
12 mo.
(continued)
Program
-94-
Table 4B (continued)
Investigator Organization a
Proposal
Number
Contract
Date
Contract
Period

Study of OH + C10 Le Bras
-Continuation of 82-412 Parkinson,
Freeman,
Yoshino
Continuation of 83-449
Continuation of 82-445 C
Ravishankara,
Wine
Traub,
Chance
CNRS Orleans
Harvard U.
83-488
83-486
Georgia Tech. 84-499
Smithsonian
Astrophysical
Laboratory at
Harvard
Continuation of 82-410 c Solomon, deZafra
Continuation of 82-401
PossibleClimatic Effect of Atmospheric Trace
Wang
SUNY Stony
Brook
Silver, Kolb Aerodyne
Researchp
Inc.
AER, Inc.
83-489
83-467
84-494
84-518
Gases
Continuation of 83-465
Absorption Cross Section of H0
2
NO
2
High Resolution
IRSpectroscopy of HOCI
Incorporation of
Chemistry INTO u. OF
Sze
Steimle
Lafferty
Brasseur
AER, Inc.
U. of Oregon
NBS
Institute d'Aeronomie
Spatiale
84-523
84-509
84-501
84-505
Berlin 3D Model
Continuation of 83-456
GAGE, Barbados Station
Stratospheric Trace Gas
Measurements Using
Matrix Isolation FTIR
Analysis
Atmospheric Aerosol from
Astronomical Data
Continuation of 82-439
Pyle
Simmonds
Griffith
Clark
Zander
RAL
Private
Max Planck,
Minz
U. of
Kentucky
U. of Liege
84-511
84-515
84-526
84-530
84-517
Program
Continuation of 83-467
Analysis of Data on
Stratospheric Nitrogen
Species
Continuation of 83-468
Investigator
Solomon, deZafra
Stokes,
Johnson,
Pearson
Brasseur
-95-
Table 4B (continued)
Organization a
SUNY
Stony Brook
Proposal
Number
84-521
Battelle
Northwest
84-493
Tnstitute d'Aeronomie
Spatiale
84-534
6/20/84 6 mo.
6/28/84 12 mo.
6/29/84 12 mo.
7/2/84
7/3/84
12 mo.
12 Mo.
-7/9/84 12 mo,
10/3/84 12 mo.
10/3/84 12 mo.
10/10/84 12 mo.
10/18/84 12 mo.
10/24/84 12 mo.
11/14/84 12 moo
11/24/84 12 moo
1/2/85 12 moo
1/21/85 12 moo
1/22/85 24 moo
(continued)
Contract
Date
Contract
Period
1/29/85 8 mo.
2/22/85 12 mo.
3/13/85 12 mo.

Participation in GAGE
Meetings
A Duplicate Single-Axis
Platform
Fraser CSIRO 85-540
Traub, Chance Smithsonian
Astrophysical
Laboratory at
Atkinson
Harvard
U. of Calif.,
Riverside
84-537
84-531 Gas Phase Reactions of
CIONO 2 monitoring of Ozone
Profile by Ground-Based
Lidar
Balloon Lidar
Measurements of OH and 0
3
Continuation of 83-484
Line Studies Using TuFIR
Spectrometer
High Resolution
Submillimeter Balloon
Spectroscopy
Continuation of 83-489
Kinetic Study of the
Reactions of N
2
0
5
Megie
Heaps
Taylor,
Roscoe
Evenson
Bonetti,
Carli
Traub, Chance
Le Bras
Service d'Aeronomie
NASA -
Goddard
Oxford U.
NBS-Boulder
U. Florence,
CNR-IROZ
Smithsonian
Astrophysical
Laboratory at
Harvard
CNRS,
84-510
84-508
84-532
84-533
85-543
85-444
85-545
-96-
3/18/85
3/22/85
4/19/85
5/10/85 pending - pending pending pending pending - pending
9 mo.
12 mo.
12 mo.
5 mo.
-
-
-
(continued)

Table 4B (continued)
Program Investigator Organization a
Proposal
Number
Contract
Date
Contract
Period
- Feasibility Study of
C10 Column Measuremt
MAP GLOBUS Support
Burnett Florida
Atlantic-U.
85-547 pending
Pommereau Service d'Aeronomie
85-550 pending - a. Abbreviated affiliations are expanded under study descriptions in Table 3. b. Contract extended. c. Work continued in a follow-on contract. d. Subcontract, see Woods 82-403. e. Subcontract, see Woods 82-432.
June 1, 1985

Table 5
PUBLICATIONS FROM WORK SUPPORTED BY CIMOROFLUOROCARBON MANUFACTURERS a
Alexander Grant & Company
1. Environmental Analysis of Fluorocarbons FC-1.1, FC-12, and FC-22, February
5, 1976.
2. Environmental Analysis of Fluorocarbons FC-11, FC-12, and
FC-22--Manufacturing Chemists Association, July 8, 1977.
3. 1977 world Production and Sales of Fluorocarbons FC-11 and FC-12, June
26, 1978.
4. 1978 World Production and Sales of Fluorocarbons FC-11 and FC-12, July 24,
1979.
5. 1979 World Production and Sales of Fluorocarbons FC-11 and FC-12, May 12,
1980.
6. 1980 World Production and Sales of Fluorocarbons FC-11 and FC-12, May 1,
1981.
7. United States Production and Sales of Chlorofluorocarbons FC-11 and FC-12 from 1976 through 1980, Chemical Manufacturers Association, Inc., September
22, 1981.
8. Carbon Tetrachloride Consumption in Production of Chlorofluorocarbons FC-11 and FC-12, Chemical Manufacturers Association, Inc., July 23, 1982.
9. 1981 World Production and Sales of Fluorocarbons FC-11 and FC-12,
Chemical Manufacturers Association, August 25, 1982.
10. 1982 World Production and Sales of Fluorocarbons FC-11 and FC-12, Chemical
Manufacturers Association, May 12, 1983.
11. 1983 Production and Sales of Chlorofluorocarbons CFC-11 and CFC-12,
Chemical Manufacturers Association Fluorocarbon Program Panel, October 22,
1984.
Allied Corporation
1. Statistical Modeling of Total Ozone Measurements with an Example Using Data from Arosa Switzerland-, W. J. Hill and P. N. Sheldon, Geophys. Res. Lett., 21
(12), 541-4 (1975).
2. Analyzing Worldwide Total Ozone for Trends, W. J. Hill, P. N. Sheldon, and
J. J. Tiede, Geophys. Res. Lett., 4 (1), 21-4 (1977).
3. Quantifying the Threshold of Stratospheric Ozone Trend Detection Using Time
Series Analysis, P. N. Sheldon, J. J. Tiede, and W. J. Hill, Proc.
Fifth Conf. Probability Statistics (Am. Meterol. Soc.), 234-9 (1977). aRefereed publications plus selected reports issued by CKA.
-98-
Allied Corporation (continued)
Table 5 (continued)

4. Ozone Trend Detectability: Update and Discussion, J. J. Tiede, P. N.
Sheldon, and W. J. Rill, Atmos. Environ., 13 (7), 999-1003 (1979).
5. Analyzing Total Ozone for Natural and Man-Made Trend Variability, L. Bishop and W. J. Hill, Geophys. Res. Lett., 9 (4), 485-8 (1982).
6. Bayesian Probability Calculations for Stratospheric Ozone Modifications, L.
Bishop and W. J. Hill, J. Geophys. Res., 89 (D2), 2589-94 (1984).
P. Ausloos, National Bureau of Standards
1. Decomposition of N20 Over Particulate Matter, R. E. Rebbert and P. A.,
Geophys. Res. Lett., 5 (9), 761-4 (1978).
4. J. Bailey, University of Maryland
1. Benefits, Costs, and Risks of CFC Controls, M. J. B., ms. of paper presented at Air Pollution Control Association national meeting, Philadelphia, Pa., June
21-6, 1981.
2. Risks, Costs,-and Benefits of Fluorocarbon Regulation, M. J. B., Am. Econ.
Rev., 77 (2), 247-50 (1982).
J. Ballard, Rutherford Appleton Laboratory
1. Experimental Determination of the Temperature Dependence of Nitrogen
Broadened Line Widths in the 1  0 Band of HC1, J. B., W. B. Johnston, P. H.
Moffat, and D. T. Llewellyn-Jones, draft ms.
D. S. Berger and F. Urbach, Temple University
1. A Climatology of Sunburning Ultraviolet Radiation, D. S. B. and F. U.,
Photobiol. Photochem., 35 (2), 187-92 (1982).
J. W. Birks, University of Colorado (Formerly University of Illinois)
1. Studies of Reactions of Importance in the Stratosphere. 1. Reaction of
Nitric Oxide With Ozone, J. W. B., B. Shoemaker, T. J. Leck, and D. M. Hinton J.
Chem. Phys., 65 (12), 5181-5 (1976).
2. Studies of Reactions of Importance in the Stratosphere. II. Reactions
Involving Chlorine Nitrate and Chlorine Dioxide, J. W. B., B. Shoemaker, T.
J. Leck, R. M. Borders, and L. J. Hart, J. Chem. Physe, 66 (10), 4591-9
(1977).
3. Studies of Reactions of Importance in the Stratosphere. III. Rate Constant and Products of the Reaction Between C10 and H0
2
Radicals at 298 K, T. J.
Leck, J-E. L. Cook, and J. W. B., J. Chem. Phys., 72 (4), 2364-73 (1980).
Table 5 (continued)
J. We.-Birks, University of Colorado (continued)
4. Studies of Reactions of Importance in the-Stratosphere. IV. Rate
Constant.for the Reaction of C1 + HOC1  HC1,+ Cl0 over the Temperature Range
243-365 K, J-E. L. Cook, C. A. Ennis, T. J. Leck, and J. We B.,J. Chem. Phys.,.74
(1), 545-9 (1981).
5. Products of the Reaction Between C1 and HOC1, J-Z. L. Cook, C. A. Ennis, T.
J. Leck, and J. We Be, J. Chem. Phys., 75 (1), 497-8 (1981).

6. Formation of Oxygen Atoms in the Reaction of Chlorine Atoms with Ozone J.
W. Vanderzanden and J. W. B., Chem. Phys. Lett., 88 (1), 109-14 (1982).
7. High Precision Measurements of Activation Energies Over Small Temperature
Intervals: Curvature in the Arrhenius Plot for the Reaction NO + 0
3
 N0
2
+
0
2
, R. A. Borders and J. We Be, J. Phys. Chem., 86 (17), 3295-302 (1982).
8. Kinetics Of C1
2
(B 3
∏
(0 +
-
)  X 1

+ g
) Chemiluminescence in the Reactions of C1
with C1
2
0, C10
2
, and 0
3
, J. W. Vanderzanden and J. W. B., draft ms.
9. Studies of Reactions of Importance in the Stratosphere. V. Rate Constants for the Reactions 0 + N0
2 
NO + 0
2
and 0 + C10  C1 + 0
2
at 298 K, A. P.
Ongstad and J. We Be, J. Chem. Phys., 81 (9), 3922-30 (1984).
10. Applications of a New Laboratory Source of Gaseous HOC1. I. Product of
Distribution in the Cl + HOC1 Reaction and Equilibrium Constant for the
Reaction C1
2
0 + H
2
0 = 2 HOC1, C. A. Ennis and J. W. B., J. Phys. Chem., 89
(1), 186-91 (1985).
A. Bonetti, University of Florence, and Be Carli, Istituto di Ricerca
sulle onde Elettromagnetiche, Italy
1. New Measurements of Stratospheric Composition Using Submillimetre and
Infrared Emission Spectroscopy, He Je Bangham; A. B., R. H. Bradsell, B. C., J.
E. Harries, F. Mencaraglia, D. G. Moss, S. Pollitt, E. Rossi, and N. R. Swann, draft ms.
2. Fourier Spectroscopy of the-Stratospheric Emissioni-B. C., F. Mencaraglia, and A. Be, Int. J. Infrared millimeter Waves, 1 (2), 263-76 (1980).
3. New Assignments in the Submillimeter Emission Spectrum of the Stratosphere,
Be C. F. Mencaraglia, and A. B., Int. J. Infrared Millimeter Waves, 3 (3),
385-94 (1982).
4. Phase Error Correction in F. T. Spectroscopy of Spectra with Positive and
Negative Intensities, B. C., F. Forni, and F. Mencaraglia, Int. J. Infrared
Millimeter waves, 3 (4), 529-40 (1982).
5. Submillimeter Detection of Stratospheric OH and Further Line Assignments in the Stratospheric Emission Spectrum, Be C., F. Mencaraglia, A. B., B. Me
Dinelli, and F. Forni, Int. J. Infrared Millimeter Waves, 4 (3), 475-88
(1983).
Table 5 (continued)
A. Bonetti, University of Florence, and B. Carli, Istituto di Ricerca
sulle Onde Elettromagnetiche, Italy (continued)
6. Atlas of Stratospheric Submillimeter Lines. I. The 7-20 cm -1 Interval, M.
G. Baldecchi, B. C., F. Mencaragliai and M.' Carlotti,.J. Geophys. Res., 89
(D7),. 11689-704 (1984).
7. The High Resolution Spectrum of Ozone Between 8-cm -1 and 150 cm -1 , M.
Carlotti, G. Di Lonardo, L. Fusina, A. Trombetti, A. B., B. C., and F.
Mencaraglia, J. Mol. Spectrosc., 107 (1), 84-93 (1984).
8. The Pure Rotation Spectrum of Nitrogen Dioxide between 10 and 80 cm -1 , B. Co,
9. Submillimeter High-Resolution FT Spectrometer for Atmospheric Studies,. B.
C., F. Mencaraglia, and A. B., Appl. Opt., 23 (15), 2594-603 (1984).
M. Carlotti, F. Mencaraglia, A. Mahmoudi, C. Camy-Peyret, and J. M. Flaud,
Mol. Phys., 51 (6), 1505-9 (1984).

10. Detection of Atomic Oxygen and Further Line Assignments in the Far Infrared
Stratospheric Spectrum, B. C.,F. Mencaraglia, A. B., M. Carlotti, and I. G.
Nolt, draft ms.
G. Brasseur, Institut dlAeronomie Spatiale, Belgium.
1. Implication for Stratospheric Composition of a Reduced Absorption Cross
Section in the Herzberg Continuum of Molecular Oxygen, G. B., A. de Rudder, and P. C. Simon, Geophys. Res. Lett., 10 (1), 20-3 (1983).
2. Acetonitrile in the Atmosphere, G. B., E. Arijs, A. de Rudder, D. Mevejans, and J. Ingels, Geophys. Res. Lett., 10 (8), 725-8 (1983).
3.
Ozone and Temperature Trends Due to the Injection of Trace Species in the
Atmosphere, G. B., Aeron. Acta A, No. 288 (1984)
4. Ozone in the 21st Century: Increase or Decrease? A. De Rudder and G. B.,
Aeron. Acta A, No. 291 (1984).
5. Is Hydrogen Cyanide (HCN) a Progenitor of Acetonitrile (CH
3
CN) in the
Atmosphere. G. B., R. Zellner, A. De Rudder, and E. Arijs, Geophys. Res.
Lett. 12 (3), 117-20 (1985).
6.
Detection of the Response of ozone in the Middle Atmosphere to Short-Term
SolarUltraviolet Variations, G. M. Keating, G. B., J. Y. Nicholson, III, and
A. De Rudder, draft ms.
7. Stratospheric Response to Chemical Perturbations, G. B., A. De Rudder, and
C. Tricot, draft ms.
_101

Table 5 (continued)
F. Bruner, Urbino University
1. Calibration Method for the GC Analysis of Halocarbons in Atmospheric Samples
Using Permeation Tubes and an Electron-Capture Detector, G. Crescentini, F.
Mangani, A. R. Mastrogiacomor and F.B., J. Chromatogr., 204, 44S-51 (1981).
2. Occurrence of P-21 (CHC12F) in the Troposphere, G. Crescentini and F. B.,
Ann. Chim. (Rome), 70 (11-12), 631-6 (1980).
3. Determination of CHFC1
2
(CFC 21) in the Tropospherep G. Cresc entini and F.
B., J. Fluorine Chem., 16 (6), 621-2 (1980)..
4. Determination of Halocarbons in Air by Gas Chromatography-High Resolution
Mass Spectrometry, F. B., G. Crescentini, and F. Mangani, Anal. Chem., 53
(6), 798-801 (1981).
5. Past Determination of Some Halocarbons in thwAtmosphere by Gas
Chromatography. High Resolution Mass Spectrometry, G. Crescentini, F.
Mangani, A. R. Mastrogiacomo, A. Cappiello, and F. B., J. Chromatogr., 280,
146-51 (1983).
6. See 39 under Rasmussen.
7. Conclusive Quantitative Data About the Presence of FC-21 in the Atmosphere,
G. Crescentinie F. Manganit A. Ro mast-rogiacomo, A. Cappiello, and F. B., draft ms.
H. L. BUijS, Bomem, Inc.
1. Simultaneous Measurement of the Volume Mixing Ratios of HC1 and HF in the
Stratosphere, H. L. B., G. L. Vail, G. Tremblay, and D. J. W. Kendall, Geophys.
Res. Lett., 7 (3), 205-8 (1980).
2. Stratospheric N0
2
and Upper Limits of CH
3
C1 and C
2
H6 from Measurements at
3.4 m, D. J. W. Kendall and H. L. B., Nature, 303, 221-2 (1983).
3. Stratospheric HF Mixing Ratio Profiles in the Northern and Southern
Hemispheres, J. H. Park, D. J. W. Kendall, and H. L. B., J. GeophXs. Res.,
89 (W), 11645-53 (1984).
M. J. Campbell, Washington State University
1. Halocarbon Decomposition by Natural Ionization, M. J. C., Geophys. Res.
Lett., 3 (11), 661-4 (1976).
2. Reply to comments by F. C. Fehsenfeld and D. L. Albritton on preceding paper [Geophys. Res. Lett., 4 (1), 61-3 (1979)], M. J. C., Geophys. Res.
Lett., 4 (1), 64 (1977).

Table 5 (continued)
Chemical Manufacturers Association Fluorocarbon Program Panel
World Production and Release of Chlorofluorocarbons,.11,,and 12 Through 1978,
August 6, 1979.
World Production and Release of Chlorofluorocarbons 11 and 12 Through 1979, May
23, 1980.
World Production and Release of Chlorofluorocarbons 11 and 12 Through 1980,
Chemical manufacturers-Association Fluorocarbon-Program Panelf July 29, 1981.
World Production and Release of Chlorofluorocarbons 11 and 12 through 1981,
Chemical Manufacturers Association Fluorocarbon Program Panel, September 15,
1982.
S. CMA CFC-11 and CFC-12 Production and Release Data [World through 19821,
Chemical Manufacturers Association Fluorocarbon Program Panel, June, 1983.
6. Production and Release of Chlorofluorocarbons 11 and 12 based on Reported Data
Through 1983, Chemical Manufacturers Association Fluorocarbon Program Panel,
October, 1984.
M. A. A. Clyne, Queen Mary College, England
Reaction Kinetics Involving Ground X 2
Π
and-Excited A 2

+ Hydroxyl Radicals. Part 1.
Quenching Kinetics of OH A 2

+ and Rate Constants for Reactions of OH X 2
Π
with
CH
3
CCl
3
and COs, M. A. A. C. and P. M. Holt, J. Chem. Soc. Faraday Trans. 2, 75
(3) 569-81 (1979).
2. Reaction Kinetics Involving Ground X 2
Π
and Excited A 2

Part 2. Rate Constants for Reactions of OH X 2
П
+ Hydroxyl Radicals.
with Halogenomethanes and Halogenoethanes, M. A. A. C. and P. M. Holt, J. Chem. Soc. Faraday Trans. 2, 75 (3),
582-91 (1979).
3. Kinetic Studies of Free Radical Reactions by mass Spectrometry. I. The
Reactions
SO + N0
2
and CIO + No, M. A. A. C. and A. J. MacRobert, Int. J. Chem. Kinet.,
12 (2), 79-96 (1980).
R. A. Cox, AERE Harwell, Englan
1. Kinetics of Chlorine oxide Radicals Using Modulated Photolysis. Part 2. C10 and ClOO Radical Kinetics in the Photolysis Of C1
2
+ 0
2
+ N
2
Mixtures, R. A.
C., R. G. Derwent, A. E. J. Eggleton, and H. J. Reid, J. Chem Soc. Faraday
Trans. 1, 75 (7), 1648-66 (1979).
2. Product Formation in the Association Reaction of C10 with N0
2
, Investigated by Diode Laser Kinetic Spectroscopy, R. A. Co, Je Po Burrows,'and G. B.
Coker, Int. J. Chem. Kinet., 16 (4), 445-67 (1984).

Table 5 (continued)
Re A. Cox, AERE Harwell, Enaland (continued)
3. Novel UV Product Spectra in the Photolysis of Chlorine Dioxide, R. A.
Barton, R. A. C., and To J. Wallington, J. Chem. Soc. Faraday Trans. 1, 80
(10), 2737-43 (1984).
J. A. Coxon Dalhousie University., Canada
1. Absolute Absorption Cross Sections at High Resolution in the A 2
Πi
- X 2
Πi
Band System of C10, So A. Barton, J. A. C., and U. K. Roychowdhury, Can. J.
Phys., 62 (5), 473-86 (1984).
D. M. Cunnold, F. No Alyea, R. Go Prinn, Massachusetts Institute of Technology and Georgia Institute of Technology
1. The Impact of Stratospheric Variability on Measurement Programs for Minor
Constituents, R. Go P., F. N.Ao, and Do Me Co, Bull. Am. Meteorol. Soc., 57
(6), 686-94 (1976).
Meteorological Control of Lower Stratospheric Minor Species Variations:
An observational Example, F. No A. and D.M. C., Atmos. Environ., 12
(6-7), 1075-80 (1978).
3. Meterorological. Constraints on Tropospheric Halocarbon and Nitrous oxide
Destructions by Siliceous Land Surfaces, F. N. A., D. M. C., and R. G. P.,
Atmos. Environ, 12 (6-7), 1009-11 (1978).
4. A Methodology for Determining the Atmospheric Lifetime of Fluorocarbons,
D. M. C., F. No A., and R. G. P., J. Geophys. Res., 83 (C11), 5493-500
(1978).
5. Uncertainties in Feedbacks in Simple Climate models and Their Influence on Prediction of the Climatic Impact of Fluorocarbons, R. G. P., F. N.
A., C. A. Cardelino, and D. M. C., draft ms.
6. Comment on "Measurement Of CC13F and CC14 at Harwell over the Period
January 197S-November 1977, D. M. C., F. N. A., and R. G. P., Atmos.
Environ., 14 (5), 617-18 (1980)*
7. The Atmospheric Lifetime Experiment. 1. Introduction, Instrumentation, and Overview, R. Go P., R. A. Rasmussen, R. D. Rosen, P. G. Simmonds, F.
N. A., C. A. Cardelino, A. J. Crawford, D. M. C., P. J. Fraser, and J. E.
Lovelock, J. Geophyse Res*, 88 (C13), 8353-67 (1983).
8. The Atmospheric Lifetime Experiment. 3. Lifetime Methodology and
Application to Three Years Of CFC1
3
Data, D. M. C., R. G. P., R. A.
Rasmussen, P. Go Simmonds, F. No A., and C. A. Cardelino, J. Geophys.
Res., 88 (C13), 8379-400 (1983).
-104-

Table 5 (continued)
D. M. Cunnold, F. N. Alyea, R. G. Prinn, Massachusetts Institute of Technology and Georgia Institute of Technology (continued)
9. The Atmospheric Lifetime Experiment. 4. Results for CF
2
C1
2
Based on Three
Years of Data, D. M. C., R. Go P., R. A. Rasmussen, P. G. Simmonds, F. N. A., and
C. A. Cardelino, J. Geophyso- Res., 88 (C1
3
), 8401-14 (1983).
10. The Atmospheric Lifetime Experiment. So Results for CH3CC13 Based on Three
Years of Data, R. G. P., R. A. Rasnussen,, P. G. Simmonds, F. N. A., D. M.
C., and B. C. Lane, J. Geophyso Reso, 88 (C13), 8415-26 (1983).
11. See 5 under P. G. Simmonds.
D. D. Davis, Georgia Institute of Technology (Formerly University of Maryland)
1.
CH
2
C1
2
A Temperature Dependent Kinetics Study of the Reaction of OH with CH
, CHC1
3
, and CH
3
3
Cl,
Br, D. D. D., G. Machado, B. Conaway, Y. O., and R. Watson,
J. Chem. Phys., 65 (4), 1268-74 (1976).
2. A Temperature Dependent Kinetics Study of the Reraction of off With CH
2
ClF,
CHC1
2
F, CHClF
2
, CH
3
CC1
3
, CH
3
CF
2
Cl
2
and CF
2
ClCFCl
2
, R. T. Watson, Go Machado,
B. Conaway, So Wagner, and Do Do Do, J. Physo Chem., 81 (3), 256-62 (1977).
3. High Resolution Absorption Cross Sections for the A 2
Π
- X 2
Π
System of Cl0, P.
H. Wine, A. R. Ravishankara, D. L. Philen, D. D. D., and R. T. Watson,
Chem.Phys. Lett, 50 (1), 101-6 (1977) (8/15/77).
E. I. du Pont de Nemours & Company, Inc. l. Atmospheric Stability of Fluoroalkanes - Implications for Ozone Depletion,
R. L. McCarthy and J. P. Jesson, Symposium on Fluorine Chemistry, Kyoto, Japan,
August 26, 1976.
2. Measurement of the Reaction Rate Of CFC1
3
with Atmosphere-Like Ions, R. Go
Hirsch, Atmos. Environ., 10-(9), 703-5 (1976). Comment, F. Co Pehsenfeld,
Do L. Albritton, et al., Ibid., 11 (3), 283-4 (1977)o Reply-, R. Go Ho,
284-5.
3. Laboratory Microwave Spectrum of ClON0
2
and Evidence for the Existence of
ClONO, R. Do Suenram, Do R. Johnson, Lo Co Glasgow, and P. Z. Meakin,
Geophys. Res. Lett., 3 (10), 611-14 (1976)1 3 (12), 758 (1976).
4. The Fluorocarbon-Ozone Theory. 1. Production and Release, World Production and Release Of CC13F and CC12F2 (Fluorocarbons 11 and 12) through 1975, R.
L. McCarthy, F. A. Bower, and J. Po Jesson, Atmos. Environ., 11 (6), 491-7
(1977).
5. The Fluorocarbon-Ozone Theory. II. Tropospheric Lifetime, An Experimental
Estimate of the Tropospheric Lifetime Of CC1
3
F, J. P. Jesson, P. Meakin, and
L. C. Glasgow, Atmos. Environ., 11(6), 499-508 (1977).
-105-

Table 5 (continued)
E. I. du Pont de Nemours a Company, Inc. (continued)
6. Photodecomposition of Chloromethanes Adsorbed on Silica Surfaces, P.
Ausloos, R. E. Rebbert, and L.C. Glasgow, J. Rese Nato Bure Stand., A, 82: (1),
1-8.
7. A one-Dimensional Model of Atmospheric Transport and Photochemistry, P.
Meakin, C. Miller, R. G. E. Franks, and J. P. Jesson, draft ms.
8. World Production and Release of Chlorofluorocarbons 11 and 12 Through
1976, July 15, 1977.
9. The Stratospheric Abundance of Peroxynitric Acid, J. P. Jesson, L. C.
Glasgowr D. L. Filkin, and C. Miller, Geophys. Res. Lett., 4 (11), 513-16
(1977).
10. World Production and Release of Chlorofluorocarbons 11 and 12 Through
1977, July 17, 1978.
11. The Fluorocarbon-Ozone Theory. Ill. Fluorocarbon Mixing and Photolysis.
The Effects of Eddy Diffusion and Tropospheric Lifetime on CC1
3
F and
CC1
2
F
2
Tropospheric Mixing Ratios, P. Meakin, P. So Gumermarr, L. C.
Glasgow, and J. P. Jesson, Atmos. Environ., 12 (6-7), 1271-85 (1978).
12. The Fluorocarbon-ozone Theory. IV. Fluorocarbon Mixing and Photolysis.
The Effects of Eddy Diffusion and Tropospheric Lifetime on Stratospheric
Odd Chlorine Mixing Ratios, L. C. Glasgow, P. So Gumerman, P. Meakin, and
J. P. Jesson, Atmos. Environ., 12 (11), 2159-72 (1978).
13. The Fluorocarbon-Ozone Theory. V. One-dimensional Modeling of the
Atmosphere, C. Miller, P. Meakin, R. G. E. Franks, and J. P. Jesson,
Atmos. Environ., 12 (12) 2481-2500 (1978).
14. The Fluorocarbon-Ozone Theory. VI. Atmospheric Modeling-Calculation of the Diurnal Steady State, C. Miller, Do L. Filkin, and J. P. Jesson,
Atmos. Environ., 13 (3), 381-94 (1979).
15. Extended Theory of Tandem Electron Capture Detectors, J. D. Lee and R. G.
Hirsch, Atmos. Environ., 13 (9), 1305-9 (1979).
16. The Stratospheric Abundance of Hypochlorous Acid (HOCl), L. C. Glasgow,
J. P. Jesson, D.L. Filkin, and C. Miller,,Planet. Space Sci., 27 (8),
1047-54 (1979).
17. Temperature Dependent Absorption Cross-Sections for Formaldehyde (CH
2
0):
The Effect of Formaldehyde on Stratospheric Chlorine chemistry, A. M.
Bass, L. C. Glasgow, C. Killer, J. P& Jesson, and D. L. Filkin, Planet.
Space Sci., 28 (7), 675-9 (1980).
18. The Fluorocarbon-Ozone Theory. VII. one-Dimensional Modeling. An
Assessment of
Anthropogenic Perturbations, C. Miller, J, M. Steed, Do L- Filkin, and J. P.
Jesson, Atmos. Environ., 15 (5), 729-42 (1981).
Table 5 (continued)
E. I. du Pont de Nemours & Company & Inc. (continued)

19. Two-Dimensional Model Calculations of Stratospheric HC1 and C10, J. M.
Steed, C. Miller, Do L. Filkin, and J. P. Jesson, Nature,,-2a8,. 46-1-4
(1980.).
20. Time Series Search for Trend in Total Ozone Measurements, D. S. St. John,
S. P. Bailey, We He Fellner, J. M. Minor, and R. D. Snee, J. Geophys.
Res., 86 (CS), 7299-311 (1981).
21. Studies on the ozone Depletion Hypothesis by Chlorofluorocarbons:
Two-Dimensional Stratospheric Modelling and Implications for
Stratospheric Chemistry, C. Miller, J. M. Steed,-EL. Filkin, and J.P.
Jesson, J. Fluorine Cheme, 16 (6), 623 (1980).
22. Time Series Analysis of Stratospheric Ozone, D. S. St.,John, S. P.
Bailey, We He Fellner, J. M. Minor, and R. D. Snee, Commun. State Theor.
Methods, All (12), 1293-333 (1982).
23. A Two-Dimensional Model of Stratospheric Chemistry and Transport, C.
Miller, Do L. Filkin, A. J. Owens, J. M. Steed and J. P. Jesson, Jo
Geophyso Res., 86 (C12), 12039-65 (1981).
24. Two-Dimensional Model Calculations of Potential Ozone Perturbation by
Chlorofluorocarbons, J. M. Steed, A. J. Owens, C. Miller, D. L. Filkin, and J. P. Jesson, Nature, 295, 308-11 (1982).
25. The Atmospheric Lifetimes of CFC 11 and CFC 12, A. J. Owens, J. M. Steed,
C. Miller, D. L. Filkin, and Jo P. Jesson, Geophys. Reso Lett., 9 (6),
700-3 (1982).
26. The Potential Effects of Increased Methane on Atmospheric Ozone, A. J.
Owens, J. Me Steed, D' L. Filkin, C. Miller, and J. P. Jesson, Geophys.
Res. Lett., 9 (9), 1105-8 (198;).
27. Potential Man-made Changes to the Ozone Content and Thermal Structure of the Atmosphere, A. J. Owens, Co He Hales, Do L. Filkin, C. Miller, A.
Yokozeki, J. M. Steed, and J. P. Jesson,_draft ms.
28. A Coupled One-Dimensional Radiative-Convective Chemistry-Transport Model of the Atmosphere. I. Model Structure and Steady-State Perturbation
Calculations, A. J.
Owens, C. Be Hales, D. L. Filkin, C. Killer, Jo Me Steed, and J. P&
Jesson, J.Geophyso Res., 90 (Dl), 2283-311 (1985).
29. Stratospheric Ozone Modification by man's Influence. A. J. Owens, A.
Yokozeki, and J., M. Steed, in Hazard Assessment of Chemicals: Current
Developments, J. Saxena, edo, Academic Press,-San Diego 3,251-336 (1984).
30. Trace Gas Influences on Climate from 1850 to 1980, Do J. Wuebbles, A. J.
Owens, and C. H. Hales, J. Am Meteorolo Soco, in press&
31. Trace Gas Influence on Climate from 1980 to 2050, A. J. Owens, C. H.
Hales, and D. J. Wuebbles, J. Am. Meteorolo Soco, in press.

Table 5 (continued)
E. 1. du Pont de Nemours & Company, Inc. (continued)
32. Natural and Manmade Chlorocarbons and Chlorofluarocarbons in the
Stratosphere: Sources, Sinks, and Calculated Impact on Ozone, A. J. Owens, D.
L. Filkin, C. H. Hales, and C. Miller, J. Air Pollut. Control Assoc., in press.
33. Multiple Component Ozone Perturbation Calculations: The Base Case and
High Chlorine Scenarios, A. J. Owens, D. A. Fisher, C. H. Hales, and M.
McFarland, draft ms.
34. See 1 under ICI Americas Inc.
D. E. Harsch, Washington State University
1. Evaluation of a Versatile Gas Sampling Container Design, D. E. H., Atmos.
Environ., 14 (9), 1105-7 (1980).
J. E. Harries, National Physical Laboratory, England
1. See 1 under Bonetti.
2. Stratospheric H
2
0, H. W. Ellsaesser, J. E. H., D. Kley, and R. Penndorf,
Planet. Space Sci., 28 (8), 827-35 (1980)'.
3. See 1 under Pyle.
Hoechst AG
1. Global Distribution of Fluorocarbons, 0. Klais and H. J. Fink, Ber.
Bunsenges. Phys. Chem., 82 (11),11,47-50 (1978),
2. Heterogeneous Photolysis of Fluorocarbons Adsorbed on Artificial and
Natural Dusts and Sand Samples, 0. Klais and M. F. Feser, Hoechst
Internal Report, 1978.
C. J. Howard, NOAA Boulder
1. Kinetics of the Reaction Of H0
2
with N0
2
, C. J. H., J. Chemo Phys., 67
(11), 525a-63 (1977).
2. Kinetics of the Reaction of H0
2
with NO, C. J. H. and K. M. Evenson,
Geophys. Res. Lett., 4 (10), 437-40 (1977).
3. Temperature Dependence of the Reaction of H0
2
+ NO  OH + N0
2
, C. J. H.,
J. Chem. Phys., 71 (6), 2352-9 (1979).
4. Temperature Dependence of the Reaction of C10 and H0
2
Radicals, R. M.
Stimpfle, R. A. Perry, and C. J. H., J. Chem. Phys., 71 (12), 5183-90
(1979).
-108-

Table 5 (continued)
C. J. Howard, NOAA Boulder (continued)
5. Kinetics of the Reaction of H0
2
with Ozone, M. S. Zahniser and C. J. Her
J. Chem. Phys., 73 (4), 1620-6 (-1980)._-
6. Yields of H0
2
in the Reaction of Hydrogen A toms with Ozone, C. J. He and
B. J. Finlayson-Pitts, J. Chem. Phys.,. 72 (6),,-3842-3 (1980).
7. Kinetic Study of the Equilibrium H0
2
+ N0 = O + N0
3
and the
Thermochemistry of H0
2
1 C. J. H.,. J. Am. Chem. Soc.,_,.102 (23) 6937-41
(1980).
8. Tunable Diode Laser Measurement-of Nitrous Oxide in Air, P. S. Connell,
R. A. Perry, and C. J. H., Geophys. Res. Lett., 7 (12), 1093-6 (1980).
9. Laser Magnetic Spectroscopy of C10 and Kinetic Studies of the Reactions of C10 with NO and N0
2
1 Y. P. Lee, R. M.. Stimpfle, R. A. Perry, J. A.
Mucha, K. K. Evenson, D. A. Jennings, and C. J. H., Into Jo Chem.
Kinet.,, 14 (6), 711-32 (1982).
10. Temperature Dependence of the Rate Constant and the Branching Ratio for the Reaction Cl + H0
2
1 Y. P. Lee and C. J. H., J. Chem. Phys., 77 (2),
756-63 (1982).
11. Room Temperature-Rate Constant for the H0
2
+ H0
2
Reaction at
Low-Pressures, G. A. Takacs and C. J. H., J. Phys. Chem., 88 (10),
2110-16 (1984).
12.
Rate Coefficient Temperature Dependence and Branching Ratio for the
OH + C10 Reaction, A. J. Hills and C. J. Her Jo Chem. Phys., 81
(10),4458-65 (1984).
13. Kinetic Study of the Reaction HO + HN0
3
, P. S. Connell and C. J. H., Int.
J. Chem. Kinet., 17 (1), 17-31 (1985).
ICI Ainericas Inc.
1. The Production and Release-to Atmosphere Of -CC1
3
F and CC1
2
F
2
(Chlorofluorocarbons CFC 11 and CFC 12), P. He Gamlen, B. C. Lane, P. M.
Midgley, and J. M. Steed, draft ms.
Istituto G. Donegani, Italy (Funded by Montefluos)
1. SCF-HF Ab Initio Study of the Reactivity of Chlorofluorocarbons: From
CFC1
3
to CHFC1
2
, G. Ranghino, J. Mole Struct., 105 (1/2), 183-9 (1983).
2. Reactivity of Fluorochloromethanes with Desert Sands, L. Benzoni and F.
Garbassi, Bero Bunsengese Phys. Chem., 88 (4), 379-82 (1984).
M. Kaufman, Emory University
1. Rate Constant of the Reaction between Chlorine Atoms and Sulfur Dioxide and Its Significance for Stratospheric Chlorine Chemistry, L. W. Strattan, R.
E. Eibling, and M. K., Atmos. Environ., 13 (1), 175-7 (1979).

Table 5 (continued)
M.Kaufman, Emory University (continued)
2. Kinetic Studies Relevant to Possible Coupling Between the Stratospheric
Chlorine and Sulfur Cycles, Re E. Eibling and M. K., Atmos. Environ., 17 (2),
429-31 (1983).
H. D. Knauth, University of Kiel, F. R. G.
1. Equilibrium Constant of the Gas Reaction C1
2
0 + H
2
0 2HOC1 and the
Ultraviolet Spectrum of HOC1, He D. K., He Alberti, and H. Clausen, J. Phys.
Chem., 83 (12), 1604-12 (1979).
C. E. Kolb, J. A. Silver,-and M. S. Zahniser, Aerodyne Research, Inc.
1. A Measurement of the vibrational strength for the V
3
Band of the H0
2
Radical, M. S. Z. and A. C. Stanton, J. Chem. Phys., 80 (10), 4951-60 (1984).
2. The Gas Phase Reaction Rate of Sodium Hydroxide with Hydrochloric Acid,
J. A. S., A. C. Stanton, Me So Z., and C. E. K., J. Phys. Chem., 88
(14), 3123-9 (1984).
3. Measurement of Atomic Sodium and Potassium Diffusion.Coefficients, J. A.
So, J. Chem. Phys., 81 (11), 5125-30 (1984).
F. Korte, Technical University of Munich, F. R. G.
1. Mineralization of Chlorofluorocarbons in the Sunlight of the Troposphere,
S. Gaeb, J. Schnitzer, H. W. Thamm, and F. K., Angew. Chem. Into Ed. Engl., 17
(5), 366 (1978).
2. Heterogeneous Photodecomposition of Fluorochlorocarbons under Simulated
Tropospheric Conditions, S. Gaeb and F. K., Ber. Bunsenges. Physe Chem.,
82 (11), 1151-3 (1978).
3. Degradation Of CC1
2
F
2
: Formation Of C0
2
upon Adsorption on Mecca Sand, Me
Bahadir, S. Gaeb, J. Schnitzer, and F. K., Chemosphere, 7 (12), 941-2
(1978).
4. Mineralization of 14CC1
2
F
2
Catalyzed by Active Surfaces, Me Bahadir, S.
Gaeb, J. Schnitzer, and F. K., Z. Naturforsch. B, 34 (6), 822-6 (1979).
So Mineralization Of CC14 and CC1
2
F
2
on Solid Surfaces, S. Gaeb, J.
Schnitzer, W. V. Turner, and F. K., Z. Naturforsch. B, 35 (8), 946-52
(1980).
K. F. Kuenzip University of Bern, and He U. Duetsch, Federal Institute of
Technology, Zurich, Switzerland
1. Comparison of Stratospheric Ozone Profiles Retrieved from
Microwave-Radiometer and Dobson-Spectrometer Data, E. Lobsiger, K. F. K., and
H. U. D., J. Atmos. Terre Phys., 46 (9), 799-806 (1984).

Table 5 (continued)
M. J. Kurylo, National Bureau of Standards
1. Rate Constant Measurements for the Reaction Cl + CH
2
0  HC1 + CHO.
Implications Regarding the Removal of Stratospheric Chlorine, P. C. Anderson and
H. J. K., J. Phys. Chem., 83 (16), 2055-7 (1919).
2. A Flash Photolysis Resonance Fluorescence Investigation of the Reaction OH
+ CH
3
CC1
3
 H
2
0 + CH
2
CCl
3
, H. J. K., P. C. Anderson, and 0. Klais, Geophys.
Res. Lett 16 (10),i760-2 (1979).
3. An Upper Limit for the Rate Constant of the Bimolecular Reaction CH3 + 0
HO + H
2
CO at 368 K, 0. Klais, 7.C. Anderson, A.H. Laufer, and M. J. X.,
Chem. Phys. Lett., 66 (3), 598-601 1979.
2

4. A Reinvestigation of the Temperature Dependence of thw-Rate Constant for the Reaction 0 + 0
2
+ M  0
3
+ M (for M - 0
2
,  N
2
,,and Ar) by the Flash
Photolysis Resonance Fluorescence Technique, 0. Klais, P. C. Anderson, and
M. J. X., Into J. Chem. Kinetc, 12 (7),469-90 (1980).
5. Atmospheric Quenching of Vibrationally Excited 020A), 0. Klais, A. H.
Laufer, and M. J. X., J. Chem. Phys.,-73 (6),,2696-9.(1980).
6. Mechanistic Investigation of the HO + H0
2
Reaction, M. J. K., 0. Klais, and
A. H. Laufer, J. Phys. Chem., 85.(24), 3674-8 (1981).
7. A Flash Photolysis Resonance Fluorescence Investigation of the Reaction OH
+ H
2
0
2
+ H0
2
+ H
2
0, M. J. K., J. L. Murphy, G. S. Haller, and K. D. Cornett,
Into J. Chem. Kinet., 14 (10), 1149-61 (1982).
8. Rate Constant Measurements of the Reaction of Cl Atoms with Nitric Acid over the Temperature Range 240-300 X, M. J. K., J. L. Murphy, and G..L.
Knable, Chem. Phys. Lett., 94 (3), 281-4 (1983).
9. A Reinvestigation of.the Cl + ClON0
2 .
Reaction by Flash Photolysis Resonance
Fluorescence, M. J.K., G. L. Knable, and J. L. Murphy, Chemo, Phys. Lett.,
95 (1), 9-12 (1983).
10.
A Kinetics Investigation of the Gas Phase Reactions of Cl(2 p
) and OH
(X 2 ) with CH
3
CN: Atmospheric Significance and Evidence for Decreased
Reactivity Between Strong Electrophiles, M. J. K. and G. L. Knable, J. Phys.
Chem., 88 (15), 3305-8 (1984).
F. J. Lovas, National Bureau of Standards
1. The Microwave and Millimeter-Wave Spectra of Hypochlorous Acid, H. E. G.
Singbeil, W. D. Anderson, R. W. Davis,. M. C. L. Gerry, E. A. Cohen, H. M.
Pickett, F. J. L., and R. D. Suenram, J. Mol. Spectrosc., 103 (2), 466-85 (1984).
2. Millimeter Wave Spectrum of Chlorine Nitrate, R. D.,Suenram and F. J. L.,
J. Mol. Spectrosc., 105 (1/2), 351-9 (1984)-
_111-
Table 5 (continued)
J. E. Lovelock, University of Reading, England
1. Atmospheric Halocarbons and Stratospheric Ozone, J. E. L., Nature, 252,
292-4 (1974).

2. Long-range Transport of Photochemical Ozone in Northwestern Europe, Re A.
Cox, A. B. J. Eggleton, R. G. Derwent, J. E. L., and D. H. Pack, Nature,
255, 118-21 (1975).
3. Natural Halocarbons in the Air and Sea, J. E. L., Nature, 256, 193-4 (1975).
4. Photochemical Oxidation of Halocarbons in the Troposphere, R. A. Cox,, Re
G. Derwent, A. E. J. Eggleton, and J. E. L., Atmose Environe, 10 (4), 305-8
(1976).
5. Halocarbon Behavior from a Long Time Series, D. H. Pack, J. E. L., G.
Cotton, and C. Curthoys, Atmos. Environ., 11 (4), 329-44 (1977).
6. The Electron Capture Detector Theory and Practice, J. Z.- L., J. Chromatogr.
99, 3-12 (1974).
7. Methyl Chloroform in the Troposphere as an Indicator of OH Radical
Abundance, J. E. L., Nature, 267, 32 (1977).
8. Fluorotrichloromethane and Tetrachloromethane Data in the British Isles
1970-1975, J. E. L. and D. H. Pack, Health Safe Lab. Environ. Q. U. S.
Eneray Res. Dev. Adm., (April), 3-20 (1976).
9. Electron-Capture Detector: Theory and Practice. II. J. E. L. and A. J.
Watson, J. Chromatogr., 158, 123-38 (1978).
10. See 7 under D. M. Cunnold, et al.
11. See 33 under Re A. Rasmussen.
12. See 5 under P. G. Simmonds.
L. R. Martin and H. S. Judeikis, Aerospace Corporation
1. Measurement of Chlorine Atom Diffusion, H. S. J. and M. Wun, J. Chem. Phys.,
68 (9), 4123-7 (1978).
2. Chlorine Atom and C10 Wall Reaction Products, Le Re M., A. G. Wren, and M.
Wan, Into J. Chem. Kineto, 11 (5), 543-57 (1979).
3. Surface Reactions of Chlorine Molecules and Atoms with Water and Sulfuric
Acid at Low Temperatures, A. G. Wren, R. W. Phillips, and L. U. Tolentino,
J. Colloid Interface Sci., 70 (3), 544-57 (1979).
4. Heterogeneous Reactions'of Cl and C10 in the Stratosphere, L. R. M. H. S.
J. and M. Wun, J. Geophys. Res., 85 (C10), 5511-18 (1980).
-112-

Table 5 (continued)
K. Moe
1. Simultaneous Measurements of Total ozone and Aerosol Extinction, K. M., L.
Muth, and P. Crooimans, ms. for presentation at International Ozone Symposium,
Boulder, Coloo, 19800
D. G. Murcray and A. Goldman, University of Denver
1. Measurements of Stratospheric Halocarbon Distributions Using Infrared
Techniques,. W. J. Williams, J. J. Kosters, A. G., and D. G. M., Geophys. Res.
Lett., 3 (7), 379-82 (1976).
2. Statistical-Band-Model Analysis and Integrated Intensity for the 10o8 Um
Band of CF
2
Cl
2
, A. G., F. S. Bonomo, and D. G. M., Geophys. Res. Lets, 3
(6), 308-12 (1976).
3. Measurements of Stratospheric Fluorocarbon Distribution Using Infrared
Techniques, We J. Williams, J. J..Kosters, A. G., and D. G. M., Geophys.
Res. Lett., 3 (7), 379-82 (1976).
4o Measurement of Stratospheric Mixing Ratio Altitude Profile of HC1 Using
Infrared Absorption Techniques, We J. Williams, J. Jo Kosters, A. G., and
D. G. M., Geophys. Res. Lett., 3 (7), 383-5 (1976).
5. Statistical Band Model Analysis and Integrated Intensity for the 11.8 jim
Band of CFC13, A. Go, F. S. Bonomo, and D. G. M., Appl. Opt., 15 (10),
2305-7 (1976).
6o Upper Limit for Stratospheric CION0
2
from Balloon-Borne Infrared
Measurements, D. G. M., A. G., W. J. Williams, F. H. Murcray, F. S. Bonomo,
C. M. Bradford, G. R. Cook, P. L. Hanst, and M. J. Molina, Geophys. Res.
Lett, 4 .(6), 227-30 (1977).
7. Identification of the V
3
, yibration-Rotation Band Of CF
4
in Balloon-Borne infrared Solar Spectra, A. G., D. G. M., F. J. Murcray, G. R. Cook, J. W.
Van Allen, F. S. Bonomog and R. D. Blatherwick, Geophys. Res. Lett., 6 (7),
609-12 (1979).
8. Stratospheric Distribution of Chlorine Nitrate, D. G. M., A. G., F. H.
Murcray, F. J. Murcray, and W. J. Williams, Geophys,. Res. Letts, 6 (11),
857-9 (1979).
9. Handbook of High Resolution Infrared Spectra of Atmospheric Interest, D. G.
M. and A. G., CRC Press, 1981.
10. observation of New Emission Lines in the Infrared Solar Spectrum Near
12.33, 12,22, 7o38 Um, Fo Js Murcray, A. G., F. H. Murcray, C. M. Bradford, and D. G. M., Astrophys. J., 247, 97-9 (1981).
11. Analysis of the V
2
and 2v
2
-v
2
Ozone Bands from High-Resolution Infrared
Spectrap A. G., J. R. Gillis, D. G. M., A. Barbeo, and C. Secroun, J. Mole
Spectrosc., 96 (2), 279-87 (1982).
-113-
Table 5 (continued)
Do Go Murcray and A. Goldman, University of Denver (continued)
12. Analysis of the v, + V
2
+ V
3
Band Of 0
3
, A. Barbe, C. Secroun, A. G.,, and J.
R. Gillis, J. Mol. Spectrosc., 100 (2), 377-81 (1983).
13. Atmospheric Transmission in the 750-2000 cm-1 Region, D. G. M., J. Quant.
Spectrosc. Radiat. Transfer, 32 (5), 381-96 (1984).
14. High Resolution IR Laboratory Spectra, Do Go M., F. J. Murcray, A. G., F.
S. Bonomo, and R. D. Blatherwick, Appl. Opt., 23-(20), 3502 (1984).
R. W. Nicholls, York University
1. The Absorption Cross Sections and f-Values for the v" = 0 Progression of
Bands and Associated Continuum for the C10 (A 2
 i
+ X 2
 i
,) System, M. Handelman and
R. W. N., J. Quant. Spectrosc. Radiat. Transfer, 17 (4), 483-91 (1977).

M. Pagano and E. Parzen, State University of New York at Buffalo.
1. Statistical Time Series Analysis of Worldwide Total Ozone for Trends, E. P.,
M. P., and H. J. Newton, draft ms.
W. H. Parkinson and D. E. Freeman, Harvard University
1. Herzberg Continuum Cross Section of oxygen in the Wavelength Region
193.5-204.0 ZIM: New Laboratory Measurements and Stratospheric implications, A.
S. C. Cheung, K. Yoshino, W. H. P., and D. E. F., Geophys. Res. Lett., 11 (6),
580-2 (1984).
2. Herzberg Continuum Cross Section of Oxygen in the Wavelength Region
193.5-204.0 nm and Band Oscillator Strengths of the (0,0) and (1,0)
Schumann-Runge Bands, A. S. C. Cheung, K. Yoshino, W. H. P., and D. E. F.,
Can J. Phys., 62 (12), 1752-62 (1984).
L. F. Phillips, University of Canterbury, No Z.
1. Upper Limit for the Atomic oxygen Yield in the 308 nm Photolysis of HOCI, P.
J. D. Butler and L. F. P., J. Phys. Chem._, 87 (1), 183-4 (1983).
J. No Pitts, Jr., and 0. C. Taylor, University of California at Riverside
1. Fluorocarbons in the Los Angeles Basin- ' No E. Hester, Eo R. Stephens, and
O. C. T., J. Air Pollut. Control Assoc., 24 (6), 519-5 (1974).
2. Relative Rate Constants for the Reaction of 0('D) Atoms with Fluorocarbons and N
2
0 J. N. P., H. L. Sandoval, and R. Atkinson,.Chem. Phys. Lett., 29
(1), 31-4 (1974).
-114-
Table 5 (continued)
J. N. Pitts, Jr., and 0. C. Taylor, University of California at Riverside
(continued)
3. Reactions of Electronically Excited 0( 1 D) Atoms with Fluorocarbons, H. L.
Sandoval, R. Atkinson, and J. N. P.J. Photochem., 3 (4), 325-7 (1974).
4. Tropospheric and Stratospheric Chemical Sinks for Commercial Fluorocarbons,
J. N. P. and R. Atkinson, Trans. Amer. Geophys. Union, 55 (12), 1153
(1974).
5. Mechanisms of Photochemical Air Pollution, J. N. P. and B. J. Finlayson,
Angew. Chem. Into Ed. Engl., 14 (1), 1-15 (1975).
6. Fluorocarbon Air Pollutants. 11. No E. Hester, E. R. Stephens, and 0. C.
To, Atmos. Environ., 9.(6-7), 603-6 (1975).
7. Fluorocarbon Air Pollutants, Measurements in Lower Stratosphere, N. E.
Hester, E. R. Stephens, and 0. C. Top Environ. Sci. Technol., 9 (9), 875-6
(1975).
8. The Photostability of Fluorocarbons, S. Japar, J. N. P., and A. M. Winer, draft ms.
9. Background and Vertical Atmospheric Measurements of Fluorocarbon-11 and
Fluorocarbon 12 over Southern California, L. Zafonte, N. E. Hester, E. R.
Stephens, and 0. C. T., Atmos. Environ., 9, 1007-9 (1975).
10o Rate Constants for the Reaction of OH Radicals with CHF2CI, CF2Cl21 CFC13, and H
2
Over the Temperature Range 297-434 K, R. Atkinson, D. A. Hansen, and
J. N. P., J. Chem. Phys., 63 (5), 1703-6 (1975).
11. Tropospheric and Stratospheric Sinks for Halocarbons: Photooxidation, O( 1 D)
Atom and OH Radical Reactions, R. Atkinson, G. M. Brewer, J. N. P., and H.
L. Sandoval, J. Geophys. Res., 81 (33), 5765-70 (1976).
12. Fluorocarbon Air Pollutants. III. Fluorocarbon measurements in the Lower
Stratosphere, N. E. Hester, E. R. Stephens, and 0. C. To, draft ms.

13. Ultraviolet and Infrared Absorption Cross Sections of Gas Phase H0
2
NO
2
, R.
A. Graham, A. M. Winer, and J. N. P., Geophys. Res. Lett., 5 (11), 909-11
(1978).
J. A. Pyle, Rutherford Appleton Laboratory
1. The Water Vapour Budget of the Stratosphere Studied Using LIMS and SAMS
Satellite Data, R. L. Jones, J. A. P. J. E. Harries, A. M. Zavody, J. H. Russell,
III, and J. C. Gills, draft ms.
R. A. Rasmussen, Oregon Graduate Center (Formerly Washington State University)
1. Halocarbon Measurements in the Alaskan Troposphere and Lower Stratosphere,
E. Robinson, R. A. R., J. Krasnec, D. Pierotti, and M. Jakubovic, Atmos.
Environ., 11 (3) , 215-23 ( 1977) .
-115-

Table 5 (continued)
R. A. Rasmussen, Oregon Graduate Center (Formerly Washington State University)
(continued)
2. Detailed Halocarbon Measurements Across the Alaskan Tropopause, E. Robinson,
R. A. R., J. Krasnec, D. Pierottl, and M. Jakubovic, Geophys. Res. Lett., 3 (6),
323-6 (1976).
3. Global and Regional N20 Measurements, R. A. R. and D. Pierotti, Pure Appl.
Geophys., 116 (2-3), 405-13 (1978).
4. Tnterlaboratory Comparison of Atmospheric Nitrous oxide Measurements. R. A.
R. and D. Pierotti, Geophys. Res. Lett., 5 (5), 353-5 (1978).
5. Tnterlaboratory Comparison of Fluorocarbon Measurements, R. A. R., Atmos.
Environ., 12 (12), 2505-8 (1978).
6. Nitrous Oxide Measurements in the Eastern Tropical Pacific ocean, D.
Pierotti and R. A. R. draft ms.
7. F-11 and N
2
0 in the North American Troposphere and Lower Stratosphere, W. D.
Saunders, E. Robinson, D. R. Cronn, R. A. R., and D. Pieratti, Water Air
Soil Pollute, 10 (4), 421-39 (1978).
Be The Sahara as a Possible Sink for Trace Gases, D. Pierotti, L. E.
Rasmussen, and R. A. R., Geophys. Res. Lett., 5 (12), 1001-4 (1978).
9. Concentration Distribution of Methyl Chloride in the Atmosphere, R. A. R.,
L. E. Rasmussen, M. A. K. Khalil, and R. W. Dalluge, J. Geophys. Res., 85
(C12), 7350-6 (1980).
10. Measurements of CHFC1
2
(Freon 21) in Background Tropospheric Air, S. A.
Penkett, N. J. D. Prosser, R. A. R., and M. A. K. Khalil, Nature, 286,
793-5 (1980) (8/21/80).
11. Atmospheric Halocarbons: Measurements and Analyses of Selected Trace Gases,
R. A. R. and M. A. K. Khalil, Proc. NATO Adv. Study Inst. Atm. Ozone,
October 1-13, 1979, pp. 209-31.
12. CHCIF
2
(F-22) in the Earth's Atmosphere, R. A. R., M. A. K. Khalil, S. A.
Penkett, and N. J. D. Prosser, Geophys. Res. Lett., 7 (10), 809-12 (1980).
13. Atmospheric Trace Gases in Antarctica, R. A. R., M. A. K. Khalil, and R. W.
Dalluge, Science, 211, 285-7 (1981).
14. Sources of Atmospheric Trace Gases in the Southern Hemisphere, M. A. K.
Khalil and R. A. R., Atmos. Environ., 15 (7), 1331-4 (1981).
15. Interlaboratory comparison of Fluorocarbons 11, 12, Methyl Chloroform, and
Nitrous Oxide Measurements, R. A. R. and M. A. K. Khalil, Atmos. Environ.,
15 (9), 1559-68 (1981).
-116-
Table 5 (continued)
R. A. Rasmussen, Oregon Graduate Center (Formerly Washing-ton State University)
(continued)

16. Atmospheric Measurements Of CF
4
and other Fluorocarbons Containing the CF
3
Group, S. A. Penkett, N. J. D. Prosser, R. A. R., and M. A. K. Khalil, J.
Geophys. Res., 86 (C6), 5172-8 (1981).
17. Atmospheric Trace Gases Over China, R. A. R., M. A. K. Khalil, and J. S.
Chang, Environ. Sci. Technol., 16 (2), 124-6 (1982).
18. increase in the Concentration of Atmospheric Methane, R. A. Re and Me A. K.
Khalil, Atmos. Environ., 15 (5), 883-6 (1981). ~
19. Atmospheric Methane (CH4):, Trends and Seasonal Cycles, Re A. R. and M. A.
K. Khalil, J. Geophys. Res., 86 (C10), 9826-32 (1981).
20. Atmospheric Methyl Chloride, M. A. K. Khalil and R. A. R., Chemosphere, 10
(9), 1019-23 (1981).
21. Decline in the Atmospheric Accumulation Rates Of CC1
3
F, CCl
2
F
2
, and CH
3
CC1
3
,
M. A. K. Khalil and R. A. R., J. Air Pollute Control Assoc., 31 (12),
1274-5, (1981).
22. Global Atmospheric Distribution and Trend of CH3CC13, R. A. R. and M. A. K.
Khalil, Geophys. Res. Lett., 8 (9), 1005-7 (1981).
23. Increase Of CHClF
2
(F-22) in the Earth's Atmosphere, M. A. K. Khalil and R.
A. R., Nature, 292, 823-4 (1981).
24. Trends of Atmospheric Methane in the Southern Hemisphere, Pe J. Fraser, M.
A. K. Khalil, and R. A. R., Geophys. Res. Lett., 8 (10), 1063-6 (1981).
25. Differences in the Concentrations of Atmospheric Trace Gases in and Above the Tropical Boundary Layer, Re A. R. and He A. K. Khalil, Pure Apple
Geophys., 119 (5), 990-7 (1982).
26. Latitudinal Distributions of Trace Gases in and Above the Boundary Layer,
R. A. R. and M. A. K. Khalil, Chemosphere, 11 (3), 227-35 (1982).
27. Methane and Carbon Monoxide in Snow, R. A. R., M. A. K. Khalil, and S. D.
Hoyt, J. Air Pollute Control Assoc., 32 (2), 176-8 (1982).
28. Atmospheric Methyl Iodide, Re A. R., M. A. K. Khalil, R. Gunawardena, and
S. D. Hoyt, J. Geophyso Res., 87 (C4),3086-90 (1982).
29. oceanic Source of Carbonyl Sulfide (OCS), R. A. R., M. A. X. Khalil, and S.
D. Hoyt, Atmos. Environ., 16 (6), 1591-4 (1982).
30. Increases in the Atmospheric Concentrations of Halocarbons and N
2
0, R. A. R. and M. A. X. Khalil, draft ms.
-117-

Table 5 (continued)
R. A. Rasmussen, Oregon Graduate Center (Formerly Washington State University)
(continued)
31. Carbonyl Sulfide and Carbon Disulfide from the Eruptions of Mount St.
Helens, R. A. R., M. A. K. Khalil, R. W. Dalluge, S. A. Penkett, and B. Jones,
Science, 215, 665-7 (1982).
32. See 7 under D. M. Cunnold, et al.
33. Atmospheric Lifetime Experiment. 2. Calibration, R. A. R. and J. E.
Lovelock, J. Geophys. Res., 88 (C13), 8369-78 (1983).
34. See 8 under D. M.Cunnold, et al.
35. See 9 under D. M. Cunnold, et al.,
36. See 10 under D. M. Cunnold, et al.
37. See 5 under P. G. Simmonds.
38. Increase and Seasonal Cycles of Nitrous oxide in the Earth's Atmosphere, M.
A. K. Khalil and R. A. R., Tellus, 35B (3), 161-9 (1983).
39. Interlaboratory Comparison, Preparation, and Stability of CHC12F (F-21)
Samples and Standards, Re A. R., M. A. K. Khalil, G. Crescentini, F.
Mangani, A. R. Mastrogiacomo, and F. Bruner, Anal. Chem., 55 (11), 1834-6
(1983).
A. R. Ravishankara and P. H. Wine, Georgia Institute of Technology
1. The Kinetics of the Reaction of OH with CIO, A. R. R., F. L. Eisele, and P.
H. W., J. Chem. Phys., 78 (3), 1140-4 (1983).
2. Absorption Cross Sections for N0
3
between 565 and 673 nm, A. R. R. and P.
H. W., Chem. Phys. Lett., 101 (1) 73-8 (1983).
3. Kinetics of the Reaction N0
2
+ N0
3
+ M at Low Pressures and 2980K, C. A.
Smith, A. R. R., and P. H. W., J. Phys. Chem., 89 (8), 1423-7 (1985).
4. Kinetics of the Reactions of 0( 3 p) and 0( 1 D) with C1
2
Nicovich, and A. R. R., J. Phys. Chem., in press.
, P. H. W. J. M.
C. Sandorfy, University of Montreal
1. Vacuum Ultraviolet and Photoelectron Spectra of Fluorochloro Derivatives of
Methane, J. Doucet, P. Sauvageau, and C. S., J. Chem. Phys., 58 (9), 3708-16
(1973).
2. Vacuum Ultraviolet Absorption Spectra of Fluoromethanes, P. Sauvageau, Re
Gilbert, P. P. Berlow, and C. S., J. Chem Phys., 59 (2), 762-5 (1973)
(7/15/73).
-118-

Table 5 (continued)
C. Sandorfy, University of Montreal (continued)
3. Vacuum Ultraviolet Absorption Spectra of Chlorofluoromethanes from 120 to 65 nm,
R. Gilbert, P. Sauvageau, and C. S., J. Chem. Phys., 60 (12), 4820-4 (1974).
4. Vacuum Ultraviolet and Photoelectron Spectra of Fluoroethanes, P.
Sauvageau, J. Doucet, R. Gilbert, and C. S., J. Chem. Phys., 61 (1), 391-5
(1974).
5. on the Hydrogen Bond Breaking Ability of Fluorocarbons Containing Higher
Halogens, T. DiPaolo and C. S., Can. J. Chem., 52 (21), 3612-22 (1974).
6. Fluorocarbon Anaesthetics Break Hydrogen Bonds, T. DiPaolo and C. S.,
Nature, 252f 471 (1974).
7. Photoelectron and Far-Ultraviolet Absorption Spectra of
Chlorofluoro-Derivatives of Ethane, J. Doucet, P. Sauvageau, and C. S., J.
Chem. Phys., 62 (2), 355-9 (1975)o
8. Photoelectron and Far-Ultraviolet Spectra of CF3Br, CF2BrCI, and CF2Br2, J-
Doucet, R. Gilbert, Po Sauvageau, and C. S., J. Chem. Phys., 62 (2), 366-9
(1975).
9. Photoelectron and Vacuum Ultraviolet Spectra of a Series of Fluoroethers,
A. H. Hardin and C. S., J. Fluorine Chem., 5 (5), 435-42 (1975).
10. Ultraviolet Absorption of Fluorocarbonsf a Review, C. S., Atmos. Environ.,
10 (5), 343-51 (1976).
R. J. Saykally, University of California, Berkeley
1. Tone-Burst Modulated Color Center Laser Spectroscopy, C. S. Gudeman, M. H.
Begemann, J. Pfafff and R. J. S., Opt. Lett.f 8 (6), 310-12 (1983).
2. Color Center Laser Optogalvanic Spectroscopy of a Planar Hollow Cathode
Plasma, M. H. Begemann, J. Pfaff, and R. J. S., draft ms*
3. Visible Laser Optogalvanic Spectroscopy of a Hollow Cathode Plasma, J.
Pfaff, M. H. Begemann, and R. J. S., draft ms.
P. G. Simmonds
1. See 7 under D. M. Cunnold, et al.
2. See 8 under D. M. Cunnoldg et al.
3. See 9 under D. M. Cunnold, et al.
4. See 10 under D. M. Cunnold, et al.

Table 5 (continued)
P. G. Simmonds (continued)
So The Atmospheric Lifetime Experiment. 6. Results for Carbon Tetrachloride
Based on 3 Years Data, P. G. S., R. A. Rasmussen, J. E. Lovelock, F. N. Alyeap D.
M. Cunnold, R. G. Prinn, and B. C. Lane, J. Geophys. Res., 88 (C13), 8427-41
(1983).
P. M. Solomon and R. L. deZafra, State University of New York at Stony Brook
1. Chlorine Oxide in the Stratospheric Ozone Layer: Ground-Based Detection and
Measurement, A. deS. Parrish, R. L. deZ., P. M. Sol, J. W. Barrett, and E. R.
Carlson, Science, 211, 1158-61 (1981).
2. A Quasi-Continuous Record of Atmospheric Opacity at X - 1.1 mm over 34 Days at Mauna Kea Observatory, R. L. deZ., A Parrish, P. M. S., and J. W.
Barrett, Into J. Infrared Millimeter Waves, 4 ( ), 757-65 (1983).
3. A Measurement of Stratospheric H0
2
by Ground-Based Millimeter-Wave
Spectroscopy, R. L. deZ., A. Parrish, P. M. S., and J. W. Barrett, J.
Geophys. Res., 89 (D1), 1321-6 ( 1984).
4. Diurnal Variation of Stratospheric Chlorine.Manoxide: A Critical Test of
Chlorine Chemistry in the Ozone Layer, P. M. S., R. L. deZ., A. Parrish, and J. W. Barrett, Science, 224, 1210-14 (1984).
5. An Observed Upper Limit on Stratospheric Hydrogen Peroxide, R. L. deZ., A.
Parrish, J. Barrett, and P. M. S., draft ms.
Do H. Stedman, University of Michigan
1. Measurement Techniques for the ozone Layer, D. H. S., Res./Dev., January,
1976, pp. 22-4, 26.
To C. Steimle, University of Oregon
1. Double Enhancement of the Multiphoton Ionization of Nitric Oxide, To C. S. and H. T. Liou, Chem. Phys. Lett., 100 (3),30G-4 (1983).
Go M. Stokes, Battelle, Pacific Northwest Laboratories
1. Daytime Variation of Atmospheric N0
2
from Ground-Based Infrared
Measurements, J. M. Flaud, C. Camy-Peyret, D. Cariolle, J. Laurent, and G. M. S.,
Geophys. Res. Lett., 10 (11), 1104-7 (1983).
2. See 2 under R. Zander.
3. Presentation of Twentieth Century Atmospheric C0
2
Record in Smithsonian
Spectrographic Plates, G. M. S. and J. C. Barnard, draft ms.
-120-

F. Stuhl, University of Bochum
Table 5 (continued)
1. The Ultraviolet Absorption of Some Halogenated Methanes and Ethanes of
Atmospheric Interest, C. Hubrich and F. S., J. Photochem., 12 (2), 93-107 (1980).
N. D. Sze, Atmospheric and Environmental Research, Inc. (Formerly Environmental
Research & Technology, Inc.)
1. Measurement of Fluorocarbons 11 and 12 and Model Validation: An Assessment,
N. D. S. and N. F. Wu, Atmos. Environ., 10 (12), 1117-25 (1976).
2. Heterogeneous Photodecomposition of Halogenated Compounds in the
Troposphere, To Y. Kong and N. D. S., EOS Trans. Am. Geophys. Union, 50
(8), 811 (1978).
3. Stratospheric Fluorine; A Comparison Between Theory and Measurements, N. D.
S., Geophys. Res. Lett., 5 (9), 781-3 (1978).
4. Is CS
2
a Precursor for Atmospheric COS? N. D. S. and M. K. W. Ko., Nature,
278, 731-2 (1979).
5. CS
2
and COS in the Stratospheric Sulfur Budget, N. D. S. and M. K. W. Ko.,
Nature, 280, 308-10 (1979).
6. Coupled Effects of Atmospheric N
2
0 and 0
3 on the Earth's Climate, W. C. Wang and N. D. S., Nature, 286, 589-90 (1980).
7. Atmospheric ozone: Comparison of Observations with Two-Dimensional Model
Calculation, M. K. W. Ko., M. Livshits, and N. D. S., Proc. Quadrennial
Into Ozone Symp. (Boulder, CO), A84-A92 (1980).
8. Photochemistry of COS, CS
2
, CH
3
SCH
3
, and H
2
S: Implications for the
Atmospheric Sulfur Cycle N. D. S. and M. K. W. Ko., Atmos. Environ., 14
(11), 1223-39 (1980).
9. The Effects of the Rate for OH + HN0
3
and H0
2
NO
2
Photolysis on Stratospheric
Chemistry, N. D.S. and M. K. W. Ko, Atmos. Environ., 15 (7), 1301-7 (1981).
10. A 2-Dimensional Calculation of Atmospheric Lifetimes for N20, CFC-11, and
CFC-12, M. W. K. Ko and N. D. S., Nature, 297, 317-19 (1982).
11. Atmospheric Sodium Chemistry. 1. The Altitude Region 70-100 km, N. D. S.,
M.K. W. Ko, W. Swider, and 3. Murad, Geophys. Res. Lett., 9 (10), 1187-90
(1982).
12. Effect of Recent Rate Data Revision on Stratospheric Modeling, M. K. W. Ko and N. D. S., Geophys. Res. Lett., 10 (4), 341-4 (1983).
13. Atmospheric Ozone: Response to Combined Emissions of CFCs, N
2 and C0
2
, N. D. S., M. K. W. Ko, and W. C. Wang, draft ms.
0, CH
4
, NO x
,
-121-

Table 5 (continued)
N.D. Sze, Atmospheric and Environmental Research, Inc. (Formerly Environmental
Research & Technology, Inc.) (continued)
14. The Seasonal and Latitudinal Behavior of Trace Gases and Ozone as
Simulated by a Two-Dimensional model of the Atmosphere, M. K. W. Ko, N. D. S.,
M. Livshits, M. B. McElroy, and J. A. Pyle, J. Atmos. Sci., in press.
15. Diurnal Variation of C10: Implications for the Stratospheric Chemistries of ClON0
2 press.
, HOC1, and HC1, M. K. W. Ko and N. D. S., J. Geophyse Res., in
16. A Zonal Mean Model of Stratospheric Tracer Transport in Isentropic
Coordinates: Numerical Simulation for N
2
0 and HN0
3
, M. K. W. T., K. Ko
Tung, D. Weisenstein, and N. D. S., J. Geophys. Res., 90 (Dl), 2313-29
(1985).
G. A. Takacs, Rochester Institute of Technology
1. Heats of Formation and Bond Dissociation Energies of Some Simple Sulfur- and Halogen-Containing Molecules, G. A. T., J. Chem. Engo Data, 23 (2), 174-5
(1978).
2. Photoabsorption Spectra of Gaseous Methyl Bromide, Ethylene Dibromide,
Nitrosyl Bromide, Thionyl Chloride, and Sulfuryl Chloride, A. P. Uthman,
P. J. Demlein, T. D. Allston, Mo C. Withiam, M. Jo McClements, and G. A.
T., J. Phys. Chem., 82 (20), 2252-7 (1978).
3. Atmospheric Photodissociation Lifetimes for Nitromethane, methyl Nitrite, and Methyl Nitrate, W. D. Taylor, T. D. Allston, M. J. Moscato, G. B.
Fazekas, R. Kozlowski, and G. A. T., Into J. Chemo Kineto, 12 (4), 231-40
(1980).
4. Laboratory Investigations Concerning Atmospheric Chlorine, M. J.
McClements, W. D. Taylor, H.C. Withiam, T. D. Allston, G. Fazekas, and G.
A. T., draft ms.
5. Photoabsorption Spectra of Gaseous CH
2
3
SO
2
Cl, CC1
3
SC1, S0
2
ClF, and (CH
To Do Allston, and Go A. To, Jo Photochem., 18 (2), 117-23 (1982).
3
0)
SO, R. Kozlowski, G. B. Fazekas, M. C. Withiame K. Bloomer, R. Sampson,
6. See 11 under C. J. Howard.
B. A. Thrush, University of Cambridge, England
1. The Rates of Reaction Of H0
2
with HO and 0
2
Studied by Laser Magnetic
Resonance, J. P. Burrows, G. W. Harris, and B. A. T., Nature, 267, 233-4
(1977).
2. Laser Magnetic Resonance Spectroscopy and its Application to Atmospheric
Chemistry, B. A. To, Acco Chemo Reso, 14 (4), 116-22 (1981)-
3. The Absolute Intensity of the 3 Band of H0
2
, J. W. Buchanan, B. A. T., and G. S. Tyndell, Chem. Phys. Lett., 103 (2), 167-8 (1983).

Table 5 (continued)
G. C. Tiao, University of Chicago (Formerly University of Wisconsin), and G.
Reinsel, University of Wisconsin
1. Statistical Analysis of Stratospheric Ozone Data for the Detection of
Trend, Go Re, Go Co To, He No Wang, Re Lewis, and D. Nychka, Atmos.
Environ., 15 (9), 1569-77 (1981).
2. A Statistical Analysis of Total ozone Data from the Nimbus-4 BUV Satellite
Experiment, G. R., G. C. T., and R. Lewis, J. Atmos. Sci., 39 (2), 418-30
(1982).
3. Analysis of Total Ozone Data for the Detection of Recent Trends and the
Effects of Nuclear Testing During the 1960's, G. R., Geophys. Res. Lett., 8
(12), 1227-30 (1981).
4. Analysis of Upper Stratospheric Ozone Profile Data from the Ground-Based
Umkehr Method and Nimbus-4 Satellite Experiment, G. R., G. C. T., R. Lewis, and M. Bobkoski, J. Geophys. Res., 88 (C9), 5393-402 (1983).
5. Use of Statistical Methods in the Analysis of Environmental Data, G. C. T.,
Am. State, 37 (4), 459-70 (1983).
6. Analysis of Upper Stratospheric Ozone Profile Data for Trends and the
Effects of Stratospheric Aerosols, G. R., G. C. T., J. J. DeLuisi, C. L.
Mateerl A. J. Miller, and J. E. Frederick, J. Geophys. Res., 89 (W),
4833-40 (1984).
W. A. Traub and K. V. Chance, Smithsonian Astrophysical Observatory at Harvard
University
1. Stratospheric HP and HC1 Observations (15 June 1981), W. A. T. and K. V. C.,
Geophys. Res. Lett., 8 (10), 1075-7 (1981).
2. Q Branches in the Rotational Spectrum of HOC1, K. V. C. and W. A. T., J.
Quant. Spectrosc. Radiate Transfer, 29 (1), 81-4 (1983).
3. The Torsional Spectrum of Chlorine Nitrate, K. V. C. and W. A. T., J. Mole
Spectrosc., 95 (21, 306-12 (1982).
4. An Upper Limit for Stratospheric Hydrogen Peroxide, K. V. C. and W. A. T.,
J& Geophyse Rese, 89 (W), 11655-60 (1984).
G. S. Watson, P. Bloomfielde and G. W. Oehlert, Princeton University
1. Stratospheric Ozone - Observations and Data Analysis, G. S. W., Am. Stat.,
36 (3, Pt.2), 312-16 (1982).
2. A Frequency Domain Analysis of Trends in Dobson Total ozone Records, P. B.,
G. W. O., M. L. Thompson, and S. Zeger, J. Geophys. Res.,, 88 (C13),
8512-22 (1983).
3. The Association of Ozone with Meteorological Variables, P. B., M. L.
Thompson, G. S. W., and S. Zeger, draft ms.
-123-
Table 5 (continued)
G. S. Watson, P. Bloomfield, and G. W. Oehlert, Princeton University (continued)
4. A Statistical Analysis of Umkehr measurements of 32-46 km Ozone, P. B., M.
L. Thompson, and S. Zeger, J. Appl. Meteorol., 21 (12), 1828-37 (1982).

5. Methods of Analysis of Stratospheric Ozone Data, G. S. W., draft ms.
6. Trends in Dobson Total Ozone: An Update through 1982, G. W. 0., draft ms.
7. Direct Analysis of Umkehr N-Values for Trends, G.W. 0., draft MS.
8. Relative Trends in Atmospheric Temperature Profiles, G. W. 0., draft ms.
R. P. Wayne, University of Cocfard,, England
1. Relative Rate Constants for the Reactions of O( l D) Atoms with Fluorocarbons and with N
2
0, R. G. Green and R. P. W., J. Photochemo, 6 (5), 371-4 (1977).
2. Vacuum Ultra-violet Absorption Spectra of Halogenated Methanes and Ethanes,
R. G. Green and R. P. W., J. Photochem., 6 (5), 375-7 (1977).
J. R. Wiesenfeld, Cornell University
1. Production of Atomic Oxygen Following Flash Photolysis Of ClONO
2
AdlerGolden and J. R. W., Chem. Phys. Lett., 82 (2), 281-4 (1981).
, S. M.
R. Zander, University of LiegeF Belgium
1. Recent Observations of HF and HCl in The Upper Stratosphere, R. Z., Geophys.
Res. Lett., 8 (4), 413-16 (1981).
2. Simultaneous Detection of FC-11, FC-12, and FC-22, through 8 to 13
Micrometers IR Solar Observations from the Ground, R. Z., G. M. Stakes, and
J. W. Brault, Geophys. Reso Letto, 10 (7), 521-4 (1983).
3. Concentrations of Hydrogen Chloride and Hydrogen Fluoride Above the
Jungfraujoch and Haute Provence in September 1983, R. Z., G. Roland, L.
Delbouille, A. J. Sauval, and P. Marche, draft ms.
R. Zellner, University of Goettingen, F. R. G.
1. H
2
Formation in the Reaction of( 1 D) with H
2
0, R. Z., G. Wagner, and B.
Himme,, J.Phys. Chem., 84 (24), 3196-8 (1980).
2. Pressure and Temperature Dependence of the Reaction C10 + N0
2
(+ N
2
) 
ClON0
2
(+ N
2
), V. Handverk and R. Z., Ber. Bunsenges. Phys. Chem., 88 (4),
405-9 (1984).
3. See 5 under Brasseur.
-124-
June 1, 1985

Index to Table 3 by Investigator and Project Number
Investigator Project Number* Page
Alyea
"
"
75-24
76-122
77-199
(C)
(C)
(C)
65
65
65
"
"
"
"
"
"
77-213
78-251
78-252
79-281
80-323
81-361
(C)
(C)
(C)
(C)
(C)
(C)
27
27
65
27, 65
27, 65
27, 65
"
"
Anderson
"
Atkinson
Ausloos
"
Bailey
Ballard
Bangham
"
Barbe
"
Becker
Beckman
Berger
"
Birks
"
"
"
"
"
"
"
"
"
"
"
Bonetti
"
82-422
83-476
82-428
82-429
84-531
77-186
78-254
80-317
82-444
82-394
82-433
80-322
83-457
83-455
79-282
75-62
82-414
78-244
79-276
80-321
80-329
81-358
82-425
83-490
76-137
80-297
-125-
(C)
(C)
(C)
(C).
(C)
(C)
(C)
(C)
(C)
75-1 (C)
76-117A (C)
76'-117B (C)
77-192
77-222
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
27, 65
27
47
47
12
26
26
70
35
62
62
51
51
12
47
71
71
12
12
12, 26
13
35
13
13
13
13
13
13
13
48
35
(continued)

Burnett
Burrows
Campbell
Carli
"
"
"
"
Chance
"
"
"
"
Chopra
Clark
Index to Table 3 by Investigator and Project Number
(continued)
Project Number* Page Investigator
Bonetti
"
"
Bradsell
"
"
Brasseur
"
"
"
"
Bruner
"
"
82-389
82-437
85-543
82-394
82-433
80-320
82-396
83-468
84-505
84-534
78-256
80-330
81-365
(c)
(c)
(c)
(c)
(c)
48
48
48
62
62
64
64
64
65
64
48
27
36
Buijs
"
"
"
"
75-90
75-98
77-156
77-168
77-221
(c)
(c)
(c)
(c)
(c)
36, 49
49
49
36
36
85-547
80-334
75-53
76-137
80-297
82-389
82-437
85-543
80-318
81-375
82-445
83-489
(c)
(c)
(c)
(c)
(c)
(c)
(c)
48
48
46
46
46
46
50
15
27
48
35
48
Cox
"
"
Coxon
"
Crutzen
84-537
85-544
81-363
84-530
80-334
82-400
83-483
78-255
80-315
84-526
-126-
(c)
(c)
(c)
(c)
(c)
62
46
52
71
15
16
16
36
36
51
(continued)

"
DeLuisi deZafra
"
"
"
"
"
"
"
Donovan
Duetsch
Eggleton
Ehhalt
Ekstrom
Elkins
Evans
Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Cunnold
"
"
"
"
"
"
"
75-24
76-122
77-199
77-213
78-251
78-252
79-281
80-323
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
65
65
65
27
27
65
27, 65
27, 65
"
"
"
Davis
"
81-361
82-422
83-476
74-10
75-73
(C)
(C)
(C)
(C)
27, 65
27, 65
27
37
37
Evenson
Fehsenfeld
Forni
"
Fraser
"
Freeman
"
Girard
Goldman
75-87
83-466
76-130
77-225
79-278
80-316
81-362 .(c)
82-410
83-467
84-521
79-286
81-371
76-116
76-145
75-27
83-473
81-363
84-533
77-222
82-389
82-437
82-415
85-540
82-412
83-486
75-88
80-322
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
38
35
48
48
28
28
16
16
50
51
(continued)
60
60
60
60
28
50
37
71
60
60
60
60
38
50
50
38
52
-127-

Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Goldman
Grass
Griffith
Harries
Heaps
Howard
"
"
83-457
81-363
84-526
76-137
84-508
75-47
76-100
(C)
(C)
(C)
(C)
(C)
51
52
51
48
52
38
17
"
"
"
"
"
Iwagami
"
Johnson
Johnson
"
Jouve
Kaufman
"
Kinoshita
Knauth
"
Kolb
"
"
"
Komhyr
Korte
Kuenzi
77-222
77-223
79-289
80-299
82-424
82-391
82-438
82-397
82-417
84-493
79-290
76-126
77-197
83-461
77-171
77-224
81-355
82-401
83-469
84-494
81-363
77-194
81-371
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
Kurylo
"
"
Lafferty
Laufer
Le Bras
"
Lee
Lovas
Lovelock
78-233
80-307
82-402
84-501
82-402
83-488
85-545
83-480
81-350
73-1
(C)
(C)
(c)
(C)
35
17
18
39
18
56
56
56, 61
61
61
52
23
47
23
52
29
50
29
29
66
39
39
47
19, 29
20
20
39
20
21
21
21
40
53
(continued)
-128-

"
"
"
"
"
"
"
"
"
"
"
Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Lovelock
"
"
"
"
"
"
"
74-3
75-67
(C)
(C)
76-120 (C)
77-144. (C)
77-193
78-226
78-243
78-264
(C)
(C)
(C)
(C)
53
29, 53
40
29, 53
30
40
30
40
"
"
"
"
79-269
79-280
(C)
(C)
34, 43
30
"
"
"
Martin
"
Megie
Mencaraglia
"
Moe
Mohnen
Moss
"
Murcray
"
"
"
"
80-293
80-324
81-348
81-370
(C)
(C)
(C)
82-421
75-81
(C)
(C)
75-81-11 (c)
84-510
82-398
82-437
78-235
75-64
82-394
82-433
75-13
75-92
76-101
76-135
77-152
(C)
(C)
(C)
(C)
(C)
(C)
(C)
40
30
41
30
30
30
30
53
48
48
41
30
62
62
54
41
54
54
41
77-166
77-211
77-219
78-228
78-265
80-328
81-364
81-380
82-413
82-423
84-497
(C)
(C)
(C)
(C)
(c)
(C)
(C)
(C)
(C)
(C)
54
54
55
55
41
55
41
55
41
41
55
(continued)
-129-

Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Nicholls
"
"
Oehlert
"
Ogawa
"
Pagano
75-11
75-11-11
75-30b
82-409
83-477
82-391
82-438
76-106
(C)
(c)
(C)
(C)
(C)
(C)
42
42
42
74
74
56
56
72
Parkinson
"
Parzen
Pearson
Phillips
82-412
83-486
76-106
84-493
78-241
(C)
(C)
(C)
16
16
72
61
31
"
Pitts
"
"
Pollitt
"
Pommereau
"
"
Prinn
"
"
"
"
"
"
"
"
"
"
Pyle
"
Rasmussen
"
"
"
"
81-342
74-2
75-12
77-190
82-394
82-433
82-392
82-436
85-550
75-24
76-122
77-199
77-213
78-251
78-252
79-281
80-323
81-361
82-422
83-476
83-456
84-511
75-2
75-59
75-71
75-84
76-140
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
31
22
32
22
62
62
58
58
58
65
65
65
27
27
65
27, 65
27, 65
27, 65
27, 65
27
72
72
58
58
32
32
32
(continued)
-130-

Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Rasmussen
"
"
"
"
"
"
"
76-142
77-181
77-201
77-215
78-247
78-248
78-260
78-263
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
42
58
33
33
42
33
59
33
"
"
"
"
"
"
Ravishankara
"
"
"
Reinsel
"
"
"
Ridley
"
Roscoe
"
"
"
"
"
Rosen
79-279
80-308
80-325
81-356
81-376
82-416
80-295
81-368
83-449
84-499
78-250
80-304
81-374
80-328
82-393
82-434
83-484
84-532
81-377
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
83-462
76-102A (C)
76-102B (C)
77-219 (C)
(C)
(C)
33
59
33
43
33
33
22
22
22
22
73
73
73
73
59
59
55
55
61
61
62
62
34
Sandorfy
Saykally
Schuster
Shamel
Sievers
Silver
"
Simmonds
"
73-2
80-300
82-397
79-275
81-358
82-401
84-494
77-193
78-243
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
34
43
56, 61
34
13
23
23
30
30
(continued)
-131-

"
"
Stedman
"
"
Steimle
"
Stokes
"
"
Stuhl
Suenram
Swann
"
Sze
"
"
Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Simmonds
"
"
"
"
"
Skogerboe
Solomon
79-269
79-280
80-324
81-370
82-421
84-515
77-206
76-130
(C)
(C)
(C)
(C)
(C)
(C)
(C)
34, 43
30
30
30
30
34
44
60
"
"
"
"
"
77-225
79-278
80-316
81-362
82-410
(C)
(C)
(C)
(C)
(C)
60
60
60
60
60
"
"
"
"
"
"
"
"
Takacs
Taylor, F.W.
83-467
84-521
74-7
76-132
77-151
82-418
84-509
82-397
82-417
84-493
77-170
81-350
82-394
82-433
75-32
76-115
77-173
78-234
79-273
80-311
81-366
82-405
83-448
83-465
84-523
77-196
82-393
-132-
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
67
67
67
67
67
70
67
67
24
61
(continued)
60
60
44
45
45
23
23
56, 61
61
61
24
40
62
62
66
66
67

"
"
Trombetti
Urbach
"
Wang
"
Watson
"
"
"
Wiesenfeld
"
Wine
Woods
"
"
"
Yoshino
"
Young
Index to Table 3 by Investigator and Project Number
(continued)
Investigator Project Number* Page
Taylor, F.W.
"
"
Taylor, O.C.
"
Thrush
"
"
82-434
83-484
84-532
73-3
74-2
75-58
(C)
(C)
(C)
75-58-11 (c)
81-378 (C)
61
62
62
62
62
24
24
24
Tiao
"
"
"
Timmons
"
"
Traub
"
"
"
78-250
80-304
81-374
83-462
76-129
77-214
78-258
80-318
81-375
82-445
83-489
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
(C)
73
73
73
73
45
45
45
46
46
46
46
84-537
85-544
83-472
75-62
82-414
83-448
84-518
78-257
81-360
82-409
(C)
(C)
(C)
(C)
(C)
(C)
83-477
76-128 (C)
77-220
81-499
82-394
82-403
82-432
82-433
82-412
83-486
75-50
-133-
(C)
(C)
(C)
69
74
74
74
74
25
62
46
46
71
71
70
25
22
62
56, 62
56, 62
62
16
16
63
(continued)

Index to Table 3 by'Investigator and Project Number
(continued)
Investigator Project Number* Page
Young
Zahniser
"
"
"
Zander
"
"
75-86
81-355
82-401
83-469
84-494
76-141
78-232
82-395
(C)
(C)
(C)
(C)
(C)
(C)
63
47
23
47
23
63
63
63
"
"
"
Zeger
Zellner
"
82-435
82-439
84-517
83-460
77-195
80-331
(C)
(C)
63
63
63
75
25
25
" 83-478 25
__________________________________________________________
*(c) indicates completed project
June 1, 1985